WO2011021360A1 - Réactif de détection d'ion sodium, procédé de détection d'ion sodium et appareil de détection d'ion sodium - Google Patents

Réactif de détection d'ion sodium, procédé de détection d'ion sodium et appareil de détection d'ion sodium Download PDF

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WO2011021360A1
WO2011021360A1 PCT/JP2010/005000 JP2010005000W WO2011021360A1 WO 2011021360 A1 WO2011021360 A1 WO 2011021360A1 JP 2010005000 W JP2010005000 W JP 2010005000W WO 2011021360 A1 WO2011021360 A1 WO 2011021360A1
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sodium ion
ion detection
light
detection reagent
organic solvent
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PCT/JP2010/005000
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English (en)
Japanese (ja)
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恵一 木村
功司 町谷
亮 片山
英二 高橋
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株式会社神戸製鋼所
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/13—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups
    • C07C205/20—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups having nitro groups and hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C07C205/21—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups having nitro groups and hydroxy groups bound to carbon atoms of six-membered aromatic rings having nitro groups and hydroxy groups bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C07C205/23—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups having nitro groups and hydroxy groups bound to carbon atoms of six-membered aromatic rings having nitro groups and hydroxy groups bound to carbon atoms of the same non-condensed six-membered aromatic ring having two nitro groups bound to the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
    • C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
    • C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
    • C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution

Definitions

  • the present invention relates to a sodium ion detection reagent, a sodium ion detection method and a sodium ion detection apparatus using the sodium ion detection reagent.
  • examples of the compound used for detecting sodium ions include the compounds described in Patent Document 1.
  • Patent Document 1 in a calixarene composed of four phenol units, a pair of non-adjacent phenol units is crosslinked with a (CH 2 ) 2 O (CH 2 ) 3 O (CH 2 ) 2 chain, and 2, A calixarene compound is described in which a chromogenic organic group such as a 4-dinitrophenylazo group is attached. It is disclosed that this compound can be used for a transmitted light ion sensor or an optical waveguide ion sensor because it forms a color with metal ions.
  • examples of the analysis method of the components contained in the sample include the methods described in Patent Document 2 and Patent Document 3.
  • Patent Document 2 in an optical microscope, excitation light is incident, detection light is incident on a thermal lens formed by irradiating the excitation light into the sample, and diffusion of the detection light after the sample is transmitted by the thermal lens.
  • a trace analysis method is described. It is disclosed that this method enables analysis with high resolution.
  • Patent Document 3 discloses a photothermal conversion device that measures a change in characteristics of the sample caused by the photothermal effect of the sample irradiated with excitation light, and includes a measurement light irradiation unit that irradiates the sample with predetermined measurement light.
  • a photothermal conversion device comprising: a phase change measurement unit that measures a phase change of the measurement light after passing through the sample by irradiating the excitation light to the measurement light irradiation unit by optical interferometry.
  • a phase change measurement unit that measures a phase change of the measurement light after passing through the sample by irradiating the excitation light to the measurement light irradiation unit by optical interferometry.
  • the present invention relates to a sodium ion detection reagent and a sodium ion detection method and a sodium ion detection device using the sodium ion detection reagent capable of accurately detecting sodium ions even when the concentration of sodium ions in the sample is low.
  • the purpose is to provide.
  • One aspect of the present invention is a sodium ion detection reagent characterized in that it contains a compound having calix [4] arene and a chromogenic organic group capable of developing color by proton dissociation equilibrium in the molecule.
  • Another aspect of the present invention is a sodium ion detection method for detecting sodium ions in a sample, which is obtained by mixing the sample, a sodium ion detection reagent and an organic solvent, and the mixing. Separating the organic solvent containing the sodium ion detection reagent from the mixture, irradiating the separated organic solvent with excitation light, and the organic solvent irradiated with the excitation light.
  • a sodium ion detection reagent is mixed with the sample, and the excitation light is obtained by the mixing between the sodium ion detection reagent and the sodium ion.
  • Coalescence is sodium ion detection method characterized by irradiating light of wavelength absorbable.
  • Another aspect of the present invention is a sodium ion detection method for detecting sodium ions in a sample flowing in a predetermined flow path, wherein a part of the sample flowing in the flow path is branched from this line in advance.
  • the sodium ion detection reagent is introduced from the step of introducing into the provided sampling unit, the step of mixing the sample introduced into the sampling unit, the sodium ion detection reagent and the organic solvent, and the mixture obtained by the mixing.
  • a step of measuring the phase change of the measurement light transmitted through the organic solvent, and the sodium ion detection reagent is a pre-constitution according to one aspect of the present invention.
  • a sodium ion detection reagent is mixed with the sample, and the excitation light is irradiated with light having a wavelength that can be absorbed by the complex of the sodium ion detection reagent and the sodium ion obtained by the mixing. This is a method for detecting sodium ions.
  • Another aspect of the present invention is a sodium ion detection device for detecting sodium ions in a sample, wherein a reagent addition unit for adding a sodium ion detection reagent to the sample and an organic solvent are added to the sample. Separation of separating the organic solvent containing the sodium ion detection reagent from an organic solvent addition part, a mixing part for mixing the sample, the sodium ion detection reagent, and the organic solvent, and a mixture obtained by the mixing And an excitation light irradiation device that irradiates the separated organic solvent with excitation light, and a measurement light that irradiates the organic solvent irradiated with the excitation light with measurement light different from the excitation light An irradiation device and a phase change detection device that measures a phase change of the measurement light that has passed through the organic solvent, and the excitation light irradiation device uses the mixing as the excitation light.
  • a laser beam irradiation apparatus capable of irradiating light having a wavelength that can be absorbed by the complex of the sodium ion detection reagent and the sodium ion, wherein the reagent addition unit is a sodium ion detection reagent.
  • the sodium ion detection reagent according to the aspect is added with the sodium ion detection reagent.
  • Another aspect of the present invention is a sodium ion detection device for detecting sodium ions in a sample flowing through a predetermined flow path, wherein a part of the sample branched from the flow path and flowing through the flow path is provided.
  • An excitation light irradiation device that irradiates the organic solvent with excitation light, and an organic solvent that is irradiated with the excitation light is irradiated with measurement light different from the excitation light.
  • 2 is a schematic cross-sectional view showing a configuration of the sample storage unit 40.
  • FIG. 6 is a schematic cross-sectional view showing a modification of the sample container 40.
  • Ultrapure water used in semiconductor factories and the like is required to have a very low impurity concentration and high purity. Specifically, the management concentration of sodium ions in advanced semiconductor factories and the like is often about 10 ppt or less. Therefore, it is required to detect a low sodium ion concentration of about 10 ppt or less.
  • the low sodium ion as described above can be obtained only by applying the calixarene compound described in Patent Document 1 to the methods described in Patent Document 2 and Patent Document 3. It was difficult to detect the concentration.
  • the present inventors as a detection method of sodium ions, photothermal effects such as laser interference photothermal conversion measurement method capable of high sensitivity and microanalysis, that is, irradiation when excitation light is irradiated to the measurement object.
  • photothermal effects such as laser interference photothermal conversion measurement method capable of high sensitivity and microanalysis, that is, irradiation when excitation light is irradiated to the measurement object.
  • the obtained color product absorbs laser light having a wavelength of 550 to 800 nm, which is generally used as detection light with high detection efficiency in the photothermal conversion measurement method. It was difficult to detect sodium ions by this method. For this reason, even when detection light having a changed wavelength is used, it is difficult to accurately detect sodium ions when the concentration of sodium ions in the sample is low.
  • the present inventors have arrived at the present invention as follows. That is, the present invention has been made based on the results of the above studies.
  • the sodium ion detection reagent according to the present embodiment contains a compound having a calix [4] arene and a chromogenic organic group capable of developing color by proton dissociation equilibrium in the molecule.
  • Such a sodium ion detection reagent can detect sodium ions with high accuracy even when the sodium ion concentration in the sample is low. That is, the obtained sodium ion detection reagent can detect sodium ions with high selectivity and high sensitivity.
  • a sodium ion detection reagent capable of detecting sodium ions with high accuracy using a photothermal conversion measurement method is obtained. More specifically, for example, a sodium ion detection reagent that can easily absorb sodium ions, but can easily absorb excitation light different from the measurement light is obtained.
  • the calix [4] arene constituting the sodium ion detection reagent can capture sodium ions.
  • the captured sodium ions are considered to induce proton dissociation of the chromogenic organic group constituting the sodium ion detection reagent.
  • proton dissociation is induced, color formation by the color-forming organic group occurs. That is, it is considered that the sodium ion detection reagent causes the calix [4] arene to capture sodium ions, and color formation by the chromogenic organic group occurs via the captured sodium ions.
  • the calix [4] arene is not particularly limited as long as it has a cylindrical structure in which four benzene rings are bonded to each other via a methylene group and can capture sodium ions. It may be combined. Specific examples include alkyl group-substituted derivatives of calix [4] arene such as tert-butylcalix [4] arene and octylcalix [4] arene. Preferably used.
  • the chromogenic organic group is not particularly limited as long as it can develop color by proton dissociation equilibrium. Specifically, for example, it is preferable that a chromophore and an auxiliary color group capable of ionic bonding with sodium ions are bonded to a benzene ring.
  • the chromophoric organic group is preferably bonded to the hydroxyl group of calix [4] arene. That is, in the case of tert-butylcalix [4] arene, it is preferably bonded to the para-position of tert-butyl.
  • the chromophoric organic group is preferably bonded to the calix [4] arene via an ester bond.
  • a plurality of the chromogenic organic groups may be bonded to the calix [4] arene, but one bonded is preferable from the following points. That is, the compound in which one chromophoric organic group is bonded forms a phenolate ion (monovalent anion) and a sodium ion (monovalent) generated by proton dissociation when forming a complex with the sodium ion. From the viewpoint of stabilizing the charge.
  • the hydroxyl group to which the chromophoric organic group is not bonded is preferably bonded to an alkyl ester group from the viewpoint of capturing sodium ions with high selectivity.
  • the chromophore is not particularly limited as long as it can form a chromophoric organic group capable of forming a color by proton dissociation equilibrium.
  • a chromophoric organic group capable of forming a color by proton dissociation equilibrium.
  • one or a plurality of nitro groups and azo groups may be mentioned, and at least one of nitro groups and azo groups is preferable.
  • the auxiliary color group is not particularly limited as long as it can be ion-bonded with sodium ions and can be used as an auxiliary color group. Specific examples include a hydroxyl group, a carboxyl group, and an amino group, and a hydroxyl group is preferable. Further, one auxiliary color group may be bonded to the benzene ring, or a plurality of the auxiliary color groups may be bonded to each other.
  • chromophoric organic group those in which the chromophore and the auxiliary chromophore are bonded to a benzene ring can be used without limitation.
  • Specific examples include, for example, dinitrophenol. It is preferably at least one of a group having a structure and a group having an azophenol structure, and more preferably a group having a dinitrophenol structure. This is for the reason described later.
  • R 1 represents a functional group represented by the following general formula (2)
  • R 2 represents a functional group represented by the following formula (3).
  • R 3 represents —NO 2 or a functional group represented by the following formula (4).
  • the sodium ion detection reagent can detect sodium ions with high accuracy even when the sodium ion concentration in the sample is low. Further, specifically, for example, it can be used for detecting sodium ions with high accuracy in the photothermal conversion measurement method.
  • the calix [4] arene constituting the sodium ion detection reagent can capture sodium ions. Then, it is considered that the trapped sodium ions induce proton dissociation of the chromogenic organic group constituting the sodium ion detection reagent. When proton dissociation is induced in this way, color formation by the color-forming organic group occurs. Therefore, it is considered that the sodium ion detection reagent captures sodium ions and develops color with the chromogenic organic group via the captured sodium ions.
  • the sodium ion detection reagent absorbs in the near ultraviolet region (around 350 nm) in the protonated state. Exists.
  • the proton dissociation state that is, in the ion bond (salt formation) state with the sodium ion trapped in the calix [4] arene
  • the electron donating property of the generated phenolate anion increases, and the resonance of ⁇ electrons causes Since a new conjugated system is generated, it is considered that absorption shifts to the long wavelength side (red shift) due to the presence of sodium ions.
  • sodium ion can be detected with high accuracy, that is, with high selectivity and high sensitivity by this red shift.
  • a sodium ion detection reagent having a group having a dinitrophenol structure as the chromogenic organic group is preferable. This is preferable from the following points. This is preferable because the acid dissociation constant of the phenolic hydroxyl group having a dinitrophenol structure, which is an auxiliary color group, is large.
  • the absorption spectrum change before and after proton dissociation is suitable for the wavelength of excitation light (for example, 447 nm) of a device using a photothermal conversion measurement method, for example, a laser interference photothermal conversion device. That is, there is almost no absorption before proton dissociation and it is colorless, but after proton dissociation, the absorption maximum wavelength exists in the vicinity of 420 nm.
  • a sodium ion detection reagent having a group having a dinitrophenol structure as the color-forming organic group is preferable from the viewpoint that synthesis is relatively easy.
  • the sodium ion detection reagent only needs to contain the compound, and may contain other compounds as long as it does not inhibit the detection of sodium ions.
  • the sodium ion detection reagent may be composed of the compound.
  • the method for synthesizing the compound contained in the sodium ion detection reagent is not particularly limited as long as the compound having the above-described configuration can be synthesized. Specifically, for example, the synthesis methods described in the following examples can be mentioned.
  • the sodium ion detection reagent is mixed with an organic solvent and an aqueous solution sample in which the presence of sodium ions and the like are to be detected. If sodium ions are mixed in the sample, the sodium ion detection reagent captures sodium ions. Is extracted into the organic solvent. If sodium ions are not mixed in the sample, a sodium ion detection reagent in which sodium ions are not captured is extracted into the organic solvent. Sodium ions can be detected by measuring a sodium ion detection reagent (an organic solvent containing a sodium ion detection reagent) extracted into the organic solvent, for example, by performing a photothermal conversion measurement method or the like.
  • the organic solvent is not particularly limited as long as it can dissolve the sodium ion detection reagent and is incompatible with the sample, for example, water.
  • Specific examples include benzene, toluene, chloroform, dichloromethane, dichloroethane, diethyl ether and the like. Of these, dichloroethane is preferable and 1,2-dichloroethane is more preferable in consideration of toxicity and boiling point of the solvent.
  • the pH of the sodium ion aqueous solution sample mixed with the organic solvent containing the sodium ion detection reagent is preferably 7 to 9, and particularly preferably 9.
  • the red shift suitably occurs.
  • sodium ion can be suitably detected by performing a photothermal conversion measurement method or the like.
  • This pH may be adjusted, for example, by adding a pH adjuster.
  • the pH adjuster is not particularly limited as long as it can be dissolved in the sodium ion aqueous solution sample to adjust the pH and does not react with the sodium ion detection reagent. Specific examples include trishydroxymethylaminomethane-hydrochloric acid buffer (Tris buffer).
  • FIG. 1 is a configuration diagram showing a configuration of a sodium ion detector 1 using a photothermal conversion measurement method according to an embodiment of the present invention.
  • the sodium ion detector 1 includes an excitation light irradiation device 10, a measurement device 20, a dichroic mirror 17, and a sample storage unit 40.
  • an organic solvent containing a sodium ion detection reagent as described above is stored as a measurement object.
  • the excitation light irradiation device 10 is for irradiating the measurement object accommodated in a predetermined position of the sample accommodation unit 40 with excitation light.
  • the excitation light irradiation device 10 includes an excitation light source 12, a spectrometer 14, a modulator 16, a condenser lens 18, and a mirror 19.
  • the excitation light source 12 can irradiate the measurement object with light having a wavelength that can be absorbed by the complex of the sodium ion detection reagent and the sodium ion, for example, excitation light having a wavelength of 365 to 532 nm. If it is, it will not be specifically limited. Specifically, for example, a xenon lamp that outputs white light, a mercury lamp that outputs ultraviolet light, a 450 nm semiconductor laser diode, a 405 nm semiconductor laser diode, a 488 nm semiconductor laser diode, a 457 nm, a 488 nm, a 514 nm Ar laser device, and a 450 to 500 nm Examples include a solid-state laser device.
  • the spectroscope 14 is not particularly limited as long as it can split the light output from the excitation light source 12.
  • the modulator 16 is not particularly limited as long as it can modulate the dispersed light into a suitable excitation light Le.
  • the condensing lens 18 is not particularly limited as long as the modulated excitation light Le can be condensed on the measurement object in the sample container 40.
  • the mirror 19 is not particularly limited as long as it reflects the excitation light Le and guides the excitation light Le to the sample in the sample container 40.
  • the excitation light irradiation device 10 splits the light output from the excitation light source 12 with the spectroscope 14 and modulates the light split with the modulator 16 to obtain suitable excitation light Le. Then, the light is condensed by the condensing lens 18 and reflected by 90 ° on the mirror 19 to guide the excitation light Le to the measurement object in the sample container 40. Then, the excitation object absorbs this excitation light and generates heat. The refractive index of the measurement object changes by the amount of temperature change due to this heat generation.
  • the measuring device 20 measures the refractive index by measuring light irradiation device that irradiates the measuring object with measuring light Lm for measuring the refractive index of the measuring object, and a phase change of the measuring light Lm. It consists of a phase change detection device.
  • the measurement device 20 includes a measurement light source 22 and necessary optical systems, a photodetector 36, and a signal processing device 38.
  • the measurement light source 22 is not particularly limited as long as it can irradiate the measurement object with measurement light having a wavelength of 550 to 800 nm, for example.
  • a frequency-stabilized He—Ne laser light generator with an output of 1 mW, a frequency-stabilized diode laser with an external resonator of 700 to 800 nm, and the like can be mentioned.
  • measurement light having a wavelength of 550 to 800 nm is also preferable from the viewpoint that the wavelength is in a region that is transparent to the solvent and in which a frequency stabilized laser can exist. As shown in FIG.
  • the measurement light emitted from the measurement light source 22 is subjected to adjustment of the plane of polarization by the ⁇ / 2 wavelength plate 23, and then is polarized by the polarization beam splitter 24, that is, two polarized lights orthogonal to each other, that is, The light is split into reference light Lr and measurement light Lm.
  • the reference light Lr is subjected to optical frequency shift (frequency conversion) by the acousto-optic modulator 25A, then reflected by 90 ° by the mirror 26A and input to the polarization beam splitter 28, where it is also reflected by 90 °, The light is guided to the polarization beam splitter 30.
  • the reference light Lr passes through the polarization beam splitter 30 and is guided to the dichroic mirror 17.
  • the measurement light Lm is subjected to optical frequency shift (frequency conversion) by the acousto-optic modulator 25B, then reflected by 90 ° by the mirror 26B and input to the polarization beam splitter 28, and the polarization beam splitter 28. And is guided to the polarization beam splitter 30. Then, the measurement light Lm passes through the polarization beam splitter 30 and is guided to the dichroic mirror 17.
  • the dichroic mirror 17 reflects the reference light Lr and measurement light Lm sent from the measurement device 20 by 90 ° and guides them to the sample storage unit 40, while being sent from the excitation light irradiation device 10.
  • the excitation light Le is transmitted as it is, and is guided to the sample container 40 coaxially with the measurement light Lm.
  • the sample storage unit 40 includes a measurement cell 41 and a reference cell 42 for storing the measurement object, details of which will be described later.
  • the reference cell 42 is for adjusting the optical distance with the measurement cell 41.
  • the reference light Lr and the measurement light Lm are each reflected by 90 ° by the dichroic mirror 17, the reference light Lr passes through the reference cell 42, and the measurement light Lm passes through the measurement cell 41. . Then, after passing through each cell, the reference light Lr and the measurement light Lm are reflected by the mirror 34 by 180 °, pass through the sample storage unit 40 once again, and are guided to the dichroic mirror 17. The reference light Lr and the measurement light Lm are each reflected by 90 ° by the dichroic mirror 17 and return to the polarization beam splitter 30.
  • the reference light Lr and the measurement light Lm that have returned to the polarizing beam splitter 30 are respectively reflected by 90 ° by the polarizing beam splitter 30, reflected by a plurality of mirrors 32, and joined by the polarizing beam splitter 33, and Head to the photodetector 36.
  • the reference light Lr and the measurement light Lm merged by the polarization beam splitter 33 interfere with each other due to a change in refractive index due to a photothermal effect and a change in the phase of the measurement light Lm, and the light intensity of the interference light is changed to the light.
  • the detector 36 converts it into an electrical signal (detection signal). That is, the measurement device 20 splits the light emitted from the measurement light source 22 into the reference light Lr and the measurement light Lm, and passes the reference light Lr passing through the reference cell 42 and the measurement cell 41.
  • a spectroscopic optical system that interferes with the measurement light Lm is included, and the spectroscopic optical system and the photodetector 36 constitute a phase change detection device.
  • the detection signal of the photodetector 36 is input to the signal processing device 38.
  • the signal processing device 38 captures the detection signal at a timing synchronized with the period of the modulation operation of the modulator 14. That is, sampling is performed periodically.
  • the signal processing device 38 calculates the phase change of the measurement light Lm based on the sampled detection signal, that is, the phase change caused by the measurement light Lm passing through the measurement object. Further, the signal processing device 38 creates data relating to the temporal change of the phase change, and as described later, based on the data, the change in refractive index, and the presence or absence of sodium ions in the measurement object. Judging.
  • the intensity S1 of the interference light is expressed by the following formula (5).
  • C1 and C2 are constants determined by the light transmittance with respect to the optical system such as the polarization beam splitter and the measurement object, and ⁇ is the optical path length of the reference light Lr and the optical path length of the measurement light Lm. And fb is a frequency difference between the reference light Lr and the measurement light Lm.
  • the phase difference ⁇ from the change in the interference light intensity S1 (that is, the difference between when the excitation light Le is not irradiated or when the light intensity is low and when the light intensity is high). It shows that change of is required.
  • the signal processing device 38 calculates the change in the phase difference ⁇ based on the equation (5).
  • the intensity of the excitation light Le is periodically modulated at the frequency f by the modulation operation of the modulator 14 (for example, rotation of the chopper), the light transmittance to the measurement object and the optical path length of the measurement light Lm are respectively It changes at the frequency f.
  • the optical path length of the reference light Lr is constant, the phase difference ⁇ also changes with the frequency f. Therefore, in order to measure (calculate) the change of the phase difference ⁇ with respect to the component of the frequency f (the same period component as the intensity modulation period of the excitation signal), the sampling timing of the detection signal can be synchronized with the modulation operation. It is possible to measure only the refractive index change of the liquid while removing the influence of noise having no frequency f component. This measurement improves the signal-to-noise ratio (S / N ratio) of the measurement of the phase difference ⁇ .
  • the modulation can be performed by controlling the power source of the excitation light source 12 with an electric circuit.
  • the sodium ion detector 1 can measure the measurement object if the measurement object is accommodated in the measurement cell 41 of the sample accommodating unit 40, and the measurement object is measured by replacing the measurement object for each measurement.
  • the present invention can be applied to any of the cases where measurement objects are sequentially introduced into the measurement cell 41 of the sample storage unit 40 and measured as described later.
  • FIG. 2 is a configuration diagram showing the configuration of the water quality inspection apparatus 2 that detects sodium ions in a sample flowing through a predetermined flow path.
  • the water quality inspection device 2 includes the sodium ion detection device 1 described above, and a sample (for example, a liquid such as ultrapure water or process water) that circulates in a predetermined flow path is partially collected and used as the sample. It detects sodium ions contained.
  • the water quality inspection apparatus 2 includes a branch pipe 52 branched from the flow path 51 through which the sample flows, a reagent addition section 54, a mixing section 56, and a separation section in order from the upstream of the branch pipe 52. Unit 57 and the sodium ion detector 1.
  • the branch pipe 52 is a pipe branched from the flow path 51 through which the sample flows, and includes a valve 53. A sample is introduced into the branch pipe 52 by opening the valve 53.
  • the reagent addition unit 54 is connected to the branch pipe 52 through a valve 55.
  • the reagent addition unit 54 stores a reagent solution in which the sodium detection reagent is dissolved in the organic solvent. By opening the valve 55, the reagent solution flows through the branch pipe 52. To be added.
  • the said reagent addition part 54 described what adds both the said sodium detection reagent and the said organic solvent, the addition part which adds the said sodium detection reagent, and the addition part which adds the said organic solvent are described. It may be provided separately.
  • the mixing unit 56 mixes the sample, the sodium detection reagent, and the organic solvent. Then, the separation unit 57 separates the mixture obtained by the mixing unit 56 into water derived from the sample and an organic solvent derived from the reagent solution, and causes the water to flow into the drainage tank 58.
  • the obtained organic solvent contains a sodium ion detection reagent that captures the sodium ions if the sample contains sodium ions.
  • the branch pipe 52 is connected to the sample container 40 of the sodium ion detector 1, and the organic solvent obtained is measured at a predetermined position of the sample container 40 of the sodium ion detector 1. Inflow as a thing.
  • a reference sample addition unit 60 may be connected to the sample storage unit 40 of the sodium ion detection device 1 via a valve 59.
  • a reference sample that is not excited by the excitation light Le is stored in the reference sample addition unit 60, and flows into a predetermined position of the sample storage unit 40 of the sodium ion detector 1 by opening the valve 59.
  • the sodium ion detection device 1 detects sodium ions by the above-described method using an inflowing measurement object and, if necessary, a reference sample. And after a detection, a measuring object is discharged
  • FIG. 3 is a configuration diagram showing the configuration of another water quality inspection apparatus 3 that detects sodium ions in a sample flowing through a predetermined flow path. About this water quality inspection device 3, a different part from the water quality inspection device 2 is explained.
  • the water quality inspection apparatus 3 includes a pH adjuster addition unit 65 between the sample addition unit 54 and the mixing unit 56.
  • the pH adjuster addition unit 65 is connected to the branch pipe 52 via a valve 66 and opens the valve 66 to add a pH adjuster to the liquid containing the sample flowing in the branch pipe 52. it can.
  • a backflow prevention valve 63 may be provided between the valve 53 and the sample addition unit 54. By doing so, the liquid to which the reagent solution or the pH adjusting agent is added can be prevented from flowing back into the flow path 51. That is, by providing the sodium ion detection device, it is possible to prevent impurities from being mixed into the sample flowing through the flow channel 51.
  • FIG. 4 is a schematic cross-sectional view showing the configuration of the sample container 40.
  • 4A shows a case where only the measurement cell 41 is formed
  • FIG. 4B shows a case where the measurement cell 41 and the reference cell 42 are included. 4 is different in positional relationship from FIG. Further, the measurement light Lm and the excitation light Le are actually coaxial.
  • the sample storage unit 40 includes a measurement channel 44 through which a measurement object can flow from the branch pipe 52 as shown in FIG. Further, when the reference cell 42 is provided, as shown in FIG. 4B, not only the measurement channel 44 but also a reference channel 45 for transmitting the reference light Lr is provided. For example, a reference sample may be allowed to flow into the reference channel 45 from the reference sample addition unit 60.
  • the sample container 40 is made of a material that allows the measurement light Lm, the excitation light Le, and the reference light Lr to pass therethrough and is not damaged by the measurement object or the reference sample. Specific examples include quartz and polydimethylsiloxane (PDMS).
  • PDMS polydimethylsiloxane
  • the size of the sample storage unit 40 is not particularly limited, but for example, is the following size.
  • the size in the direction perpendicular to the flow direction of the measurement flow channel 44 is, for example, a square shape having a length D1 of 5 mm.
  • the size of the measurement channel 44 in the direction perpendicular to the flow direction is, for example, a square with a length D3 of 20 mm.
  • the length D2 of the direction parallel to the flow direction of the said measurement flow path 44 is 15 mm, for example.
  • the sizes of the measurement flow channel 44 and the reference flow channel 45 are not particularly limited, and are, for example, the following sizes. Specifically, for example, the cross section of the flow path is 1 mm ⁇ 1 mm, and the length in the direction parallel to the flow direction (flow path length) is 10 mm.
  • FIG. 5 is a schematic cross-sectional view showing a modified example of the sample container 40.
  • FIG. 6 is an explanatory diagram for explaining an example of the path of each light when the sample container 40 shown in FIG. 5 is used. 6 is the same as the sodium ion detector 1 shown in FIG. 1 except that the positional relationship is different from that in FIG. 1 and that the path of each light is as shown in FIG.
  • the sample container 40 includes a control cell 46 as well as the measurement cell 41 and the reference cell 42 as shown in FIG.
  • the control cell 46 is provided with a control channel 47 for introducing a reference sample that is not excited by the excitation light Le.
  • inflow ports and outflow ports are omitted from the respective flow paths.
  • the measurement cell 41 includes a first measurement light Lm1 obtained by separating the measurement light Lm with a spectrometer 71 and a first excitation light Le1 obtained by dispersing the excitation light Le with a spectrometer 72. Permeate (Ch1). Further, in the control cell 46, as shown in FIG. 6, the second measurement light Lm2 obtained by dispersing the measurement light Lm with a spectrometer 71 and the second excitation light Le2 obtained by dispersing the excitation light Le with a spectrometer 72. Are transmitted (Ch2).
  • the reference cell 42 transmits the reference light Lr (Ref).
  • the dichroic mirror 17 here reflects the measurement light Lm, for example, light having a wavelength of 633 nm, and transmits the excitation light Le, for example, light having a wavelength of 450 nm. Therefore, the light transmitted through each cell is reflected by the dichroic mirror 17, is again transmitted through each cell, is reflected by 90 ° by the polarizing beam splitter 30, and is guided to the polarizing beam splitter 33. As shown in FIG. 6, each light guided to the polarization beam splitter 33 is first combined with the first measurement light Lm1 guided to the polarization beam splitter 33 and the reference light Lr. The combined light is guided to the first photodetector 74 of the photodetector 36.
  • the second measurement light Lm2 guided to the polarization beam splitter 33 and the reference light Lr are combined, and the combined light is guided to the second photodetector 75 of the photodetector 36. That is, the first photodetector 74 can obtain a measurement signal of the photothermal effect obtained by the interference between Ch1 and Ref, and the second photodetector 75 can obtain the photothermal energy obtained by the interference between Ch2 and Ref. An effect measurement signal can be obtained. By comparing each obtained measurement signal (taking a difference), it is possible to detect Na.
  • FIG. 7 is an explanatory diagram for explaining another example of the path of each light when the sample container 40 shown in FIG. 5 is used. 7 shows only the periphery of the polarizing beam splitter 33 and the photodetector 36, and other parts are the same as those in FIG.
  • the first photodetector 74 the first measurement light Lm1 and the second measurement light Lm2 guided to the polarization beam splitter 33 are combined, and the combined light is used as the light.
  • the light is guided to the first light detector 74 of the detector 36. That is, a photothermal effect measurement signal obtained by interference between Ch1 and Ch2 can be directly obtained, and Na can be detected as it is. Instead, in order to increase the reliability, a measurement signal of a photothermal effect obtained by interference between Ch2 and Ref is obtained in the state shown in FIG. Thereafter, in the state shown in FIG. 7B, photothermal effect measurement signals obtained by interference between Ch1 and Ref are obtained, and the measurement signals are adjusted to have the same magnitude.
  • excitation light having different wavelengths of the excitation light Le are used.
  • two or more excitation lights having different wavelengths may be used.
  • the abnormality can be found by using two or more excitation lights having different wavelengths.
  • measurement is performed using excitation light having a wavelength around 400 to 450 nm, which is the main peak, a sharp change in absorbance near the peak can be used, and high sensitivity can be expected.
  • FIG. 8 is a schematic cross-sectional view showing the sample container 40 when two excitation lights having different wavelengths of the excitation light Le are used.
  • FIG. 9 is an explanatory diagram for explaining an example of the path of each light when the sample container 40 shown in FIG. 8 is used. 9 is the same as the sodium ion detector 1 shown in FIG. 1 except that the positional relationship is different from that in FIG. 1 and that the path of each light is as shown in FIG.
  • the sample container 40 includes a control cell 46 as well as the measurement cell 41 and the reference cell 42 as in FIG.
  • the control cell 46 is provided with a control flow channel 47 for allowing the same measurement object as the measurement cell 41 to flow in.
  • inflow ports and outflow ports are omitted from the respective flow paths.
  • the measurement cell 41 transmits a first measurement light Lm1 obtained by separating the measurement light Lm with a spectrometer 71 and a first excitation light Le1, for example, an excitation light having a wavelength of 450 nm ( Ch1).
  • the control cell 46 includes a third measurement light Lm3 obtained by separating the measurement light Lm with a spectrometer 71 and a third excitation light Le3, for example, excitation light having a wavelength of 365 nm or 405 nm. (Ch3).
  • the reference cell 42 transmits the reference light Lr (Ref).
  • the dichroic mirror 17 here reflects the measurement light Lm, for example, light having a wavelength of 633 nm, and transmits the excitation light Le, for example, light having a wavelength of 450 nm. Therefore, the light transmitted through each cell is reflected by the dichroic mirror 17, is again transmitted through each cell, is reflected by 90 ° by the polarizing beam splitter 30, and is guided to the polarizing beam splitter 33. Then, each light guided to the polarization beam splitter 33 is first combined with the first measurement light Lm1 and the reference light Lr guided to the polarization beam splitter 33, as shown in FIG. The combined light is guided to the first photodetector 74 of the photodetector 36.
  • the third measurement light Lm3 guided to the polarizing beam splitter 33 and the reference light Lr are combined, and the combined light is guided to the second photodetector 75 of the photodetector 36. That is, the first photodetector 74 can obtain a measurement signal of the photothermal effect obtained by the interference between Ch1 and Ref, and the second photodetector 75 can obtain the photothermal energy obtained by the interference between Ch3 and Ref. An effect measurement signal can be obtained. By comparing each obtained measurement signal (taking a difference), it is possible to detect Na.
  • a measurement signal of the photothermal effect obtained by the interference between Ch1 and Ch3 may be obtained by the first photodetector 74.
  • R 2 represents a functional group represented by Formula (3), and R 4 represents a —OCH 2 COOH group.
  • the obtained yellow solid was dissolved in chloroform, washed twice with 1N hydrochloric acid (100 mL) and twice with ion-exchanged water (100 mL), the chloroform phase was recovered, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (ethyl acetate) to isolate the desired product.
  • R 1 represents a functional group represented by the above general formula (2)
  • R 2 represents a functional group represented by the above formula (3)
  • R 4 represents —OCH It shows the 2 COOH group.
  • the obtained sodium ion detection reagent was evaluated as follows.
  • a 5 ⁇ 10 ⁇ 5 mol / L sodium chloride (NaCl) aqueous solution was prepared as an aqueous layer component.
  • 1 ⁇ 10 ⁇ 2 mol / L, pH 8 Tris-HCl buffer was used as a solvent.
  • organic layer component 5 ⁇ 10 ⁇ 5 mol / L of the sodium ion detection reagent solution was prepared. At that time, 1,2-dichloroethane was used as a solvent.
  • FIG. 10 shows the results obtained by measuring the organic layer from which sodium ions were extracted with a spectrophotometer [Visible-ultraviolet spectrophotometer (JASCO V-550) manufactured by JASCO Corporation].
  • FIG. 10 is a graph showing the measurement results with a spectrophotometer. At that time, the vertical axis indicates absorbance, the horizontal axis indicates wavelength, and the measurement result is indicated by a curve 101.
  • the obtained sodium ion detection reagent absorbs light having a wavelength of about 450 nm when sodium ions are detected.
  • the sodium ion detection reagent emits light having a wavelength of about 450 nm. Hardly absorbs. That is, it can be confirmed that the obtained sodium ion detection reagent undergoes a large red shift in the presence of sodium ions. Therefore, by using this sodium ion detection reagent, sodium ions can be detected by spectrophotometry using a spectrophotometer, and sodium ions can be detected not only by spectrophotometry but also by the photothermal conversion measurement method described above. I understand.
  • FIG. 11 is a graph which shows the result of having examined the kind of metal ion in the measurement with a spectrophotometer.
  • the obtained sodium ion detection reagent hardly absorbed light with a wavelength of 447 nm and did not shift red with metal ions other than sodium ions. From this, it was found that the obtained sodium ion detection reagent has very high selectivity for sodium ions.
  • a sodium chloride (NaCl) aqueous solution having a sodium ion concentration in the range of 0 to 0.92 ppm (specifically, for example, 0.0, 0.046, 0.14,. 23, 0.46, 0.92 ppm).
  • NaCl sodium chloride
  • 1 ⁇ 10 ⁇ 2 mol / L, pH 9 Tris-HCl buffer was used as a solvent.
  • organic layer component 5 ⁇ 10 ⁇ 5 mol / L of the sodium ion detection reagent solution was prepared. At that time, 1,2-dichloroethane was used as a solvent.
  • each of the aqueous layer component and the organic layer component were stirred and mixed at 25 ° C., 177 rpm for 10 minutes.
  • the resulting mixture was centrifuged at 25 ° C., 15000 rpm, 10 minutes. By doing so, it separated into the organic layer and the water layer, and the sodium ion which existed in the water layer was extracted to the organic layer. That is, the organic layer from which each sodium ion was extracted corresponding to the sodium ion concentration present in the aqueous layer was measured using an absorptiometric method and a photothermal conversion measurement method, respectively.
  • FIG. 12 is a graph showing an output result (absorbance) when the absorptiometry is used and an output result when the photothermal conversion measurement method is used.
  • the vertical axis shows the output result (mV) when measured using the photothermal conversion measurement method
  • the horizontal axis shows the output result when measured using the absorptiometry, that is, at a wavelength of 447 nm. The absorbance is shown.
  • the correlation coefficient R 2 is 0.9985. This shows that the sodium ion concentration can be measured by the photothermal conversion measurement method by using the sodium ion detection reagent. It was also found that sodium ions of about 10 ppb can be detected even by using the absorptiometry, and that the water quality can be sufficiently controlled even by the absorptiometry by using the sodium ion detection reagent.
  • a sodium chloride (NaCl) aqueous solution having a sodium ion concentration in the range of 0 to 23 ppb was prepared. At that time, 1 ⁇ 10 ⁇ 2 mol / L, pH 9 Tris-HCl buffer was used as a solvent.
  • organic layer component 5 ⁇ 10 ⁇ 5 mol / L of the sodium ion detection reagent solution was prepared. At that time, 1,2-dichloroethane was used as a solvent.
  • the aqueous layer component and the organic layer component were stirred and mixed at 25 ° C., 177 rpm for 10 minutes.
  • the resulting mixture was centrifuged at 25 ° C., 15000 rpm, 10 minutes. By doing so, it separated into the organic layer and the water layer, and the sodium ion which existed in the water layer was extracted to the organic layer. That is, the organic layer from which each sodium ion was extracted corresponding to the sodium ion concentration present in the aqueous layer was measured using a photothermal conversion measurement method.
  • the measurement conditions of the photothermal conversion measurement method were such that the output of the excitation light source was 5 mW and the optical path length of the measurement cell was 10 mm.
  • FIG. 13 is a graph showing the relationship between the output result and the sodium ion concentration when the photothermal conversion measurement method is used. At that time, the vertical axis represents the output result (mV), and the horizontal axis represents the sodium ion concentration (ppb).
  • the difference between the signal intensity of the blank and the signal intensity when Na is added is defined as signal fluctuation (1 ⁇ ) as noise, the ratio is S / N, and detected when S / N exceeds 40 It was possible. That is, it is possible to detect 25 ppt of sodium ions.
  • the signal intensity of the photothermal conversion measurement method is proportional to the excitation light intensity, it is known that the intensity of the excitation light may be increased when detecting a lower concentration. Since the maximum output of the excitation light source (LD) used in the experiment was about 40 mW, the intensity of the excitation light can be increased up to four times that at the time of measurement, and thus theoretically has a sensitivity of about 6 ppt.
  • LD excitation light source
  • One aspect of the present invention is a sodium ion detection reagent characterized in that it contains a compound having calix [4] arene and a chromogenic organic group capable of developing color by proton dissociation equilibrium in the molecule.
  • a sodium ion detection reagent capable of accurately detecting sodium ions can be obtained even when the sodium ion concentration in the sample is low. That is, the obtained sodium ion detection reagent can detect sodium ions with high selectivity and high sensitivity.
  • the sodium ion detection reagent specifically, for example, a sodium ion detection reagent capable of detecting sodium ions with high accuracy using a photothermal conversion measurement method is obtained. More specifically, for example, a sodium ion detection reagent that can easily absorb sodium ions, but can easily absorb excitation light different from the measurement light is obtained.
  • the calix [4] arene constituting the sodium ion detection reagent can capture sodium ions.
  • the captured sodium ions are considered to induce proton dissociation of the chromogenic organic group constituting the sodium ion detection reagent.
  • proton dissociation is induced, color formation by the color-forming organic group occurs. That is, it is considered that the sodium ion detection reagent causes the calix [4] arene to capture sodium ions, and color formation by the chromogenic organic group occurs via the captured sodium ions.
  • the sodium ion detection reagent preferably has the following configuration.
  • the calix [4] arene is tert-butylcalix [4] arene, and the chromogenic organic group is bonded to the hydroxyl group of the tert-butylcalix [4] arene.
  • the chromogenic organic group is bonded to the hydroxyl group of the tert-butylcalix [4] arene.
  • it is.
  • sodium ions in the sample can be detected with higher selectivity and higher sensitivity.
  • the chromophoric organic group is a benzene ring bonded to a chromophore and an auxiliary chromophore capable of ionic bonding with sodium ions.
  • sodium ions in the sample can be detected with higher selectivity and higher sensitivity.
  • the chromophore is preferably at least one of a nitro group and an azo group.
  • sodium ions in the sample can be detected with higher selectivity and higher sensitivity.
  • the auxiliary color group is preferably a hydroxyl group.
  • sodium ions in the sample can be detected with higher selectivity and higher sensitivity.
  • the chromogenic organic group is preferably at least one of a group having a dinitrophenol structure and a group having an azophenol structure.
  • sodium ions in the sample can be detected with higher selectivity and higher sensitivity.
  • the compound is preferably represented by the following general formula (1).
  • R 1 represents a functional group represented by the following general formula (2)
  • R 2 represents a functional group represented by the following formula (3).
  • R 3 represents —NO 2 or a functional group represented by the following formula (4).
  • sodium ions in the sample can be detected with higher selectivity and higher sensitivity.
  • Another aspect of the present invention is a sodium ion detection method for detecting sodium ions in a sample, which is obtained by mixing the sample, a sodium ion detection reagent and an organic solvent, and the mixing. Separating the organic solvent containing the sodium ion detection reagent from the mixture, irradiating the separated organic solvent with excitation light, and the organic solvent irradiated with the excitation light.
  • a sodium ion detection reagent is mixed with the sample, and the excitation light is obtained by the mixing between the sodium ion detection reagent and the sodium ion.
  • Coalescence is sodium ion detection method characterized by irradiating light of wavelength absorbable.
  • the sample, the sodium ion detection reagent and the organic solvent are mixed, and the organic solvent containing the sodium ion detection reagent is separated from the mixture obtained by the mixing.
  • the sodium ion detection reagent capturing sodium ions present in the sample is extracted into an organic solvent. Therefore, an organic solvent containing a sodium ion detection reagent that captures sodium ions is obtained.
  • the sodium ion detection reagent that has captured sodium ions is absorbed by the excitation light, but the detection light different from the excitation light, for example, detection with high detection efficiency in the photothermal conversion measurement method as described above. Absorption of laser light having a wavelength of 550 to 800 nm, which is generally used as light, is suppressed.
  • the photothermal effect can be exerted on the sodium ion detection reagent that has captured sodium ions.
  • the organic solvent irradiated with the excitation light is irradiated with measurement light different from the excitation light, that is, light having a wavelength different from that of the excitation light, for example, measurement light having a wavelength of 550 to 800 nm,
  • measurement light having a wavelength different from that of the excitation light
  • the said measurement light hardly absorbs the said sodium ion detection reagent irrespective of the presence or absence of the said sodium ion. That is, the wavelength of the measurement light and the absorption wavelength of the sodium ion detection reagent are different.
  • sodium ions in the sample can be detected with high accuracy even when the sodium ion concentration in the sample is low, for example.
  • Another aspect of the present invention is a sodium ion detection method for detecting sodium ions in a sample flowing in a predetermined flow path, wherein a part of the sample flowing in the flow path is branched from this line in advance.
  • the sodium ion detection reagent is introduced from the step of introducing into the provided sampling unit, the step of mixing the sample introduced into the sampling unit, the sodium ion detection reagent and the organic solvent, and the mixture obtained by the mixing.
  • a step of measuring the phase change of the measurement light transmitted through the organic solvent, and the sodium ion detection reagent is a pre-constitution according to one aspect of the present invention.
  • a sodium ion detection reagent is mixed with the sample, and the excitation light is irradiated with light having a wavelength that can be absorbed by the complex of the sodium ion detection reagent and the sodium ion obtained by the mixing. This is a method for detecting sodium ions.
  • the sample without stopping the flow of the sample in the predetermined flow path, the sample is allowed to flow in the predetermined flow path, that is, online, as described above, sodium ions in the sample. Can be detected with high accuracy.
  • the excitation light preferably has a wavelength of 365 to 532 nm.
  • sodium ions in the sample can be detected with higher accuracy and stability.
  • the excitation light is preferably helium-neon laser light or semiconductor laser light.
  • excitation light for example, excitation light having a wavelength of 365 to 532 nm can be stably irradiated, and sodium ions in the sample can be detected with higher accuracy.
  • the wavelength of the measurement light is preferably 550 to 800 nm.
  • the measurement light of this wavelength is generally used as detection light with high detection efficiency in the photothermal conversion measurement method as described above.
  • the detection light of such wavelength sodium ions in the sample are used. Can be detected with higher accuracy.
  • the step of measuring the phase change includes spectroscopically dividing the reference light from the measurement light, and interfering the spectroscopic reference light and the measurement light transmitted through the organic solvent; And detecting the intensity of the light after the interference.
  • the phase change can be measured by a relatively simple method of measuring the intensity of the light after the reference light and the measurement light transmitted through the organic solvent are interfered with each other. Further, by using the reference light, the signal-to-noise ratio (S / N ratio) can be improved. Therefore, sodium ions in the sample can be easily detected with high accuracy.
  • Another aspect of the present invention is a sodium ion detection device for detecting sodium ions in a sample, wherein a reagent addition unit for adding a sodium ion detection reagent to the sample and an organic solvent are added to the sample. Separation of separating the organic solvent containing the sodium ion detection reagent from an organic solvent addition part, a mixing part for mixing the sample, the sodium ion detection reagent, and the organic solvent, and a mixture obtained by the mixing And an excitation light irradiation device that irradiates the separated organic solvent with excitation light, and a measurement light that irradiates the organic solvent irradiated with the excitation light with measurement light different from the excitation light An irradiation device and a phase change detection device that measures a phase change of the measurement light that has passed through the organic solvent, and the excitation light irradiation device uses the mixing as the excitation light.
  • a laser beam irradiation apparatus capable of irradiating light having a wavelength that can be absorbed by the complex of the sodium ion detection reagent and the sodium ion, wherein the reagent addition unit is a sodium ion detection reagent.
  • the sodium ion detection reagent according to the aspect is added with the sodium ion detection reagent.
  • the sample, the sodium ion detection reagent and the organic solvent are mixed, and the organic solvent containing the sodium ion detection reagent is separated from the mixture obtained by the mixing.
  • the sodium ion detection reagent capturing sodium ions present in the sample is extracted into an organic solvent. Therefore, an organic solvent containing a sodium ion detection reagent that captures sodium ions is obtained.
  • the sodium ion detection reagent that has captured sodium ions is absorbed by the excitation light, but the detection light different from the excitation light, for example, detection with high detection efficiency in the photothermal conversion measurement method as described above. Absorption of laser light having a wavelength of 550 to 800 nm, which is generally used as light, is suppressed.
  • the photothermal effect can be exerted on the sodium ion detection reagent that has captured sodium ions.
  • the organic solvent irradiated with the excitation light is irradiated with measurement light different from the excitation light, that is, light having a wavelength different from that of the excitation light, for example, measurement light having a wavelength of 550 to 800 nm,
  • measurement light having a wavelength of 550 to 800 nm
  • sodium ions in the sample can be detected with high accuracy even when the sodium ion concentration in the sample is low, for example.
  • Another aspect of the present invention is a sodium ion detection device for detecting sodium ions in a sample flowing through a predetermined flow path, wherein a part of the sample branched from the flow path and flowing through the flow path is provided.
  • An excitation light irradiation device that irradiates the organic solvent with excitation light, and an organic solvent that is irradiated with the excitation light is irradiated with measurement light different from the excitation light.
  • the sample without stopping the flow of the sample in the predetermined flow path, the sample is allowed to flow in the predetermined flow path, that is, online, as described above, sodium ions in the sample. Can be detected with high accuracy.
  • the laser beam irradiation device is capable of irradiating light having a wavelength of 365 to 532 nm. According to such a configuration, sodium ions in the sample can be detected with higher accuracy and stability.
  • the laser beam irradiation device is capable of irradiating a helium-neon laser beam or a semiconductor laser beam. According to such a configuration, excitation light, for example, excitation light having a wavelength of 365 to 532 nm can be stably irradiated, and sodium ions in the sample can be detected with higher accuracy.
  • the measuring light irradiation device can irradiate light having a wavelength of 550 to 800 nm.
  • the measurement light of this wavelength is generally used as detection light with high detection efficiency in the photothermal conversion measurement method as described above. By using the detection light of such wavelength, sodium ions in the sample are used. Can be detected with higher accuracy.
  • the phase change detection device spectrally separates the reference light from the measurement light, and the spectroscopic device that interferes with the spectroscopic reference light and the measurement light transmitted through the organic solvent, It is preferable to include a light detection device that detects the intensity of light after interference.
  • the phase change can be measured by a relatively simple method of measuring the intensity of the light after the reference light and the measurement light transmitted through the organic solvent interfere with each other. Further, by using the reference light, the signal-to-noise ratio (S / N ratio) can be improved. Therefore, sodium ions in the sample can be easily detected with high accuracy.
  • a sodium ion detection reagent capable of detecting sodium ions with high accuracy even when the sodium ion concentration in a sample is low. Moreover, the sodium ion detection method and sodium ion detection apparatus using the said sodium ion detection reagent are provided.

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Abstract

L'invention porte, selon un aspect, sur un réactif de détection d'ion sodium qui comprend un composé ayant un calyx[4]arène et un groupe organique apte à développer une couleur, qui peut développer une couleur à travers un équilibre de dissociation protonique dans la molécule. L'invention porte de manière spécifique sur un procédé de détection d'ion sodium pour détecter un ion sodium dans un échantillon, par exemple dans un procédé de mesure de conversion photothermique, une substance qui a piégé un ion sodium étant utilisée comme analyte et la substance étant mesurée au moyen du réactif de détection d'ion sodium.
PCT/JP2010/005000 2009-08-19 2010-08-09 Réactif de détection d'ion sodium, procédé de détection d'ion sodium et appareil de détection d'ion sodium WO2011021360A1 (fr)

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MARY MCCARRICK ET AL.: "Novel chromogenic ligands for lithium and sodium based on calyx[4]arene tetraesters", J. CHEM. SOC., CHEM. COMMUN., 1992, pages 1287 - 1289 *

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