JPH0387633A - Method for quantitatively determining material or ion to be incorporated during non-deionized welding and crystal oscillator coated with barrier on one surface to be used in this method - Google Patents

Abstract

PURPOSE:To make quantitative determination by coating one of both electrodes of the crystal oscillator with a barrier so as to prohibit the permeation of a non-deionized soln. via a specified insulating space and measuring the frequency while the crystal oscillator is held immersed into the non-deionized soln. CONSTITUTION:One electrode 2b of the electrodes 2a and 2b deposited by evaporation on a crystal plate 1 is coated by using the barrier formed by sealing, for example, a plastic plate 6, which is stable in the non-deionized soln., and, for example, silicone rubber 4, which are stable in the non-deionized soln., with polymer adhesive agents 3a and 3b of, for example, a silicone system, which is stable in the non-deionized soln. so as to prohibit the permeation of the non-deionized soln. to the insulating space 5, via the specified insulating space 5 while the tight contact with the electrode 2b is substantially averted. An adsorption film 7 is cast on the electrode 2a. The easy temp. control and stirring during the frequency measurement are possible in this way and the frequency is measured in the state of immersing the oscillator in the one-side barrier soln. without requiring a large-sized cell or a large volume of the non-deionized soln. and distilled water.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a method for quantifying substances or ions contained in a non-deionized solution, and a method in which one side of both electrodes used in the method is coated with a barrier and the other side is coated with a barrier. A crystal oscillator coated with an adsorption film (hereinafter simply referred to as a single-sided barrier-coated crystal oscillator)
In particular, the present invention relates to a method for on-the-spot determination of substances or ions contained in a non-deionized solution using a quartz crystal oscillator, and a single-sided barrier-coated quartz crystal oscillator used in the method.

[Prior Art] When quantifying substances or ions contained in a non-deionized solution using a crystal oscillator, if the crystal oscillator is directly immersed in the non-deionized solution, Depending on the concentration of ions in the ion solution, there is virtually no oscillation and quantification is virtually impossible, or accurate quantification is impossible, so the frequency must be measured separately in distilled water or in the gas phase. A commonly used method is to quantify the

In addition, conventionally, for example, (1) a crystal oscillator is attached to a flow cell, and distilled water is first passed through the flow cell, and then an ionic solution is passed through the flow cell, as applied to research on antigen-antibody reactions (1). (2) A method for quantifying by adsorbing it onto a sample and then measuring the frequency while flowing distilled water.
As applied to the determination of heavy metal ions, a crystal oscillator is sandwiched between two cells, one cell is filled with an ion solution, and the other cell is filled with distilled water. (3) As applied to the determination of heavy metal ions, the crystal oscillator is held horizontally and a type of cylinder is placed on only one side of the crystal oscillator. There is a known method for quantifying the frequency by attaching the ionic solution to the ionic solution and measuring the frequency.

[Problems to be Solved by the Invention] Among the above-mentioned conventional techniques, the first method uses a flow cell system and requires a large amount of solution, and is disadvantageous when adsorption and desorption are reversible reactions, and the second method is disadvantageous because of oscillation. This method takes advantage of the fact that the oscillator is insensitive to the weight on the crystal plate other than the electrode part, in other words, the crystal plate other than the electrode part does not participate in oscillation, but as the capacitance of the cell increases, the oscillator Since it is made of a thin crystal plate, there is a problem with its strength.The third method, like the second method, uses an I
This method takes advantage of the fact that it is insensitive to flL, but it has the drawbacks that temperature control is difficult and stirring is not possible.

The present invention has been made to solve the problems in the prior art described above.

The present invention is a method for quantifying substances or ions contained in a non-deionized solution by measuring the frequency using a crystal oscillator, and it is possible to easily adjust temperature and stir during frequency measurement. At the same time, the frequency can be measured while the crystal oscillator is immersed in the non-deionized solution, without the need for large cells or large amounts of non-deionized solution and distilled water. It is an object of the present invention to provide a method for quantifying contained substances and a single-sided barrier-coated crystal oscillator used in the method.

The present invention provides a method for quantifying odorants and bitter substances contained in a non-deionized solution by measuring the frequency of the crystal using a crystal oscillator. The object of the present invention is to provide a method for measuring and quantifying the frequency under such conditions, and a single-sided barrier-coated crystal oscillator used in the method.

[Means for Solving the Problems] The present invention first provides a method for quantifying substances or ions contained in a non-deionized solution using a crystal oscillator. is coated with a barrier so that the non-deionized solution does not permeate through a certain insulating space without being in substantial contact with the other electrode, an adsorption film is cast on the other electrode, and then one side of both electrodes is coated with the barrier. , a crystal oscillator whose other side is coated with the adsorption film is immersed in the non-deionized solution, and the substances or ions contained in the non-deionization solution are adsorbed or chemically bonded to the adsorption film, respectively. Or, quantifying the substance or ion contained in the non-deionized solution by measuring the change in frequency before and after chemical bonding while the single-sided barrier-coated crystal oscillator is immersed in the non-deionized solution. A method for quantifying substances or ions contained in a non-deionized solution is provided.

Second, the present invention is a crystal oscillator used in a method for quantifying substances or ions contained in a non-deionized solution, in which one of the two electrodes is fixed at a certain level without being in substantially close contact with the crystal oscillator. The object of the present invention is to provide a single-sided barrier-coated crystal oscillator, which is coated with a barrier so that the non-deionized solution does not permeate through an insulating space, and an adsorption film is cast on the other electrode.

The non-deionized solution used in the present invention is suitable for use in aqueous systems such as aqueous solutions, aqueous dispersions, aqueous emulsions, and aqueous suspensions in which it is virtually impossible to measure the frequency while the crystal oscillator is immersed therein. Examples include non-deionized water, non-deionized aqueous solutions, non-deionized aqueous emulsions, non-deionized colloidal aqueous dispersions, etc., and exclude distilled water and deionized water.

Examples of the above-mentioned non-deionized solutions include alcoholic beverages such as beer, sake, whiskey, shochu, and wine;
Drinks such as milk, coffee milk, coffee black tea 1 Japanese tea, soft drinks such as fruit juice drinks and carbonated drinks, water and sewage water, and water from rivers, lakes, and marshes, etc.

The substances contained in the non-deionized solution that can be quantified by the method of the present invention include those that are adsorbed to an adsorption film cast on the electrodes of a crystal oscillator and determined by determining the change in frequency using API. Examples include odorants, bitter substances, etc.

In the method of the present invention and the single-sided barrier coated crystal oscillator used in the method, a non-deionized solution does not pass through one of the picture electrodes of the crystal oscillator through a certain insulating space without substantially coming into close contact with the picture electrode. Barrier coated and
Cast an adsorbent film on the other electrode.

Silver or aluminum vapor-deposited electrodes can also be used as electrodes for the single-sided barrier-coated crystal oscillator used in the present invention, but they tend to dissolve in non-deionized solutions, making oscillation unstable, and are inactive. metals that can be deposited with, e.g. gold,
Electrodes such as platinum are preferred.

The method of barrier coating the electrode in the method of the present invention is not particularly limited as long as the barrier coating is applied so that the non-deionized solution does not permeate through a certain insulating space without substantially adhering to the electrode. The first embodiment will be explained with reference to FIG. 1. An electrode 2a deposited on a crystal plate 1
and 2b, such as a plastic material which is stable in the non-deionized solution, such that the non-deionized solution does not permeate through the insulating space 5 into the insulating space 5 without being in substantially intimate contact with one of the electrodes 2b of the electrodes 2b. This is done by sealing the plate 6 and a non-deionized solution-stable, e.g. silicone rubber 4 with a non-deionized solution-stable, e.g. silicone-based polymer adhesive 3a and 3b; Adsorption film 7 is cast.

In a second embodiment of the barrier coating method for electrodes, a plastic member 5 is coated with an adhesive 3 as shown in FIG.
A method of forming an insulating space 4 between the electrode 2b and the electrode 2b by a barrier formed by sealing with
For example, an insulating space 3 may be formed by providing a barrier 4 of a quartz plate integrally formed with the insulation space 3.

The certain insulating space in the above electrode barrier coating method is not particularly limited as long as the conductivity between the two electrodes is interrupted, but it is preferably 0.5 m+s to 5 m+s as the vertical distance from the electrode surface. open, more preferably 1
mm to 2 mm. The distance between the insulation spaces is 0.5+
If it is less than ++s, there is a risk that the electrical conductivity between the two electrodes will be insufficiently interrupted, and although it is possible to exceed 5 times, the space will increase meaninglessly, and it will not only be technically meaningless but also pose a problem in use. There may be cases where this occurs.

In the present invention, examples of the adsorption membrane that is cast on the electrode and that adsorbs substances contained in a non-deionized solution include immobilized bilayer membranes and polymer membranes. The polymer compound constituting the polymer membrane can be used alone, as a mixture thereof, or as a mixture of these and a low-molecular compound such as a monomer.

The immobilized bilayer membrane may be aC-XC@b (where a and b are, for example, -N (
CHi)3, SO3-POa represents a hydrophilic group moiety such as polyol or polyether, and Cj+Cl11+
and C, is an alkyl group or fluoroalkyl group having a carbon chain of C8 or more in total.

represents a hydrophobic group moiety such as an alkylene group, and X is a trialkyl type, dialkyl type and/or monoalkyl type ammonium represented by a rigid segment (representing a rigid portion) such as diphenylazomethine, biphenyl, naphthalene, anthracene group, etc. Synthetic lipids such as salts, sulfonates, carboxylic acid groups, etc. and/or C1 / phosphatidylcholine, phosphatidylserine, etc., represented by the formula: a\7 (where a, C,,C,, are as defined above) Examples include films in which natural lipids are immobilized with polymers.

As a specific example of the immobilized bilayer film used in the present invention, (1) the synthetic lipid and/or natural lipid is blended with a polymer compound such as polyvinyl chloride, polystyrene, polycarbonate, polyvinyl alcohol, or acetyl cellulose. Cast thin film; (i.e., by impregnating the pores of a filter with a microporous structure such as Millipore filter or Duraguard with a chloroform solution of the synthetic lipid and/or natural lipid and drying it;
(w) Mixing the aqueous dispersion of the synthetic lipid and/or natural lipid having a cationic hydrophilic group with an aqueous solution of an anionic polymer such as polystyrene sulfonic acid, heparin, polyvinyl sulfonic acid, polyacrylic acid, polyglutamic acid, etc. A thin film obtained by dissolving the resulting polyion complex powder in chloroform and casting it; (a polyion complex type bimolecule consisting of a lipid having an anionic hydrophilic group and a cationic polymer such as polyallylamine, polyethyleneimine, or quaternized polyaminostyrene) Membrane film; fvl Langmuir-Prodgett type cumulative membrane of the synthetic lipids and/or natural lipids; Ml(i) to (V)
Examples include a combination of and a polymer membrane; and a combination of (viQlil~輌). In the case of M+, the adverse effects of moisture can be prevented.

Examples of the polymer compounds constituting the polymer membrane used as the adsorption membrane of the present invention include organic synthetic polymer compounds, organic natural polymer compounds, inorganic synthetic polymer compounds, and inorganic natural polymer compounds. Examples of organic synthetic polymer compounds include polystyrene, polyvinyl chloride, synthetic resins, and synthetic rubber. Examples of organic natural polymer compounds include cellulose, starch, natural rubber, and protein. Examples of inorganic synthetic polymer compounds include polychlorinated phosphonitrile. Examples of inorganic natural polymer compounds include ummo, asbestos, and the like.

The polymer membrane generally acts selectively depending on the type of substance contained in the non-deionized solution.

For example, it is preferable to use γ-methyl-L-glutamate as a polymer membrane for lower fatty acid esters as odorants, and it is preferable to use polystyrene or polyvinyl chloride as a polymer membrane for low-molecular ketones. It is preferable to use polyvinyl alcohol as a polymer membrane for the carboxylic acid, and it is preferable to use polystyrene as a polymer membrane for styrene as a malodorous substance.

The polymer membrane used as an adsorption membrane that is cast on the single-sided barrier coated crystal oscillator of the present invention and chemically bonds with the ions contained in the non-deionized solution includes, for example, a polymer membrane having a functional group that bonds with the ions. Examples include molecular membranes.

The bitter substance in the present invention is not particularly limited as long as it is adsorbed to the adsorption membrane of the present invention, and includes inorganic acids.

Acidic substances such as organic acids, caustic soda, and ammonia.

Inorganic and organic basic substances such as pyridine and triethylamine, salts such as inorganic salts and organic salts, pharmaceuticals, agricultural chemicals, and the like can also be included.

Typical examples of the bitter substances include strychnine, quinine, nicotine, phenylthiourea, bababerine, caffeine, naringin, octaacetyl sucrose, and oligopeptides. The odorant in the present invention is not particularly limited as long as it is adsorbed to the adsorption membrane of the present invention.
In a broad sense, it can include fragrances, anesthetics, malodorous substances, pharmaceuticals, agricultural chemicals, etc. in addition to odorants in the narrow sense.

Representative examples of the above-mentioned odorants in the narrow sense include aliphatic alcohols such as β-ionone and octatool, kanlua, amyl acetate, vanillin, ethyl butyrate, phenol, and aldehydes.

Representative examples of the above-mentioned fragrances include anisylaldehyde, undecanol, anis alcohol, anisole, phenylethyl acetate, citral, methylsalicylate, benzyl acetate, tetrahydrogeraniol, tilpinol, and geranyl acetate.

Examples of the above-mentioned malodorous substances include ketones, amines, imines, aldehydes such as acetaldehyde, organic acids that emit malodors, sulfur compounds such as methyl mercaptan, hydrogen sulfide, methane sulfide, and methyl disulfide. Examples include styrene, mixtures thereof, various industrial waste substances that emit bad odors and mixtures thereof, substances that cause bad breath and mixtures thereof.

Regarding the above anesthetics, examples of general anesthetics (compounds having an anesthetic effect) are shown in Table 1. In Table 1, botency is a value representing the strength of the anesthetic, and here the value for tadpoles is shown.

Table 1 Anesthetic Compounds Methanol L-Probanol Butanone Diethyl Ether L-Butanol Balaldehyde Benzyl Alcohol Chloroform L-Hexanol Halosene Methoxyfuran l-octanolbentane l-nohexane l-decanol potency l,00 2.43 3.47 9.43 1.20X1.0 2.99X 104,. 4.3X 10 5.44 [Effects of the Invention] According to the present invention, firstly, in a method for quantifying substances or ions contained in a non-deionized solution by using a single-sided barrier-coated crystal oscillator and measuring its frequency, A single-sided barrier-coated quartz crystal is immersed in a non-deionized solution, allowing for easy temperature control and stirring without the need for large cells or large amounts of non-deionized solution and distilled water. By measuring the frequency in the raw state, it is possible to determine the substances contained in the non-deionized solution, such as odorants and bitter substances, or Ca'', Mg''
, Mn'', etc. can be accurately quantified on the order of nanograms (ng) as in distilled water.

[Example] Example 1 As shown in Fig. 1, AT cut 9.00Mt (z
The gold-deposited electrodes 2a and 2b of the crystal plate 1 of the crystal oscillator (
5 mmφ), dialkyl ammonium salt ions (2C, 8N"2C2) and polystyrene sulfonate ions (PSS-) are reacted at 70°C to produce a precipitate of a polyion complex, and re-precipitate. After drying, it was dissolved in chloroform and cast to a thickness of 0.5 microns to form an immobilized bilayer film.On one side of the quartz plate 1, around the electrode 2b at a distance of about 3 angles in the radial direction from the periphery. Apply the silicone polymer adhesive 3a in the circumferential direction, and apply a layer of 10 mm vertically x 10 mm horizontally x 3111 mm thick on top of it.
A circular piece 4 with a diameter of approximately 6 mm is cut out from the center of the silicone rubber plate 1, and then sealed.Then, the adhesive 3b is applied on top of the hollowed out circular piece 4 with a diameter of 0.2 to 1 mm. A plastic plate 6 was placed and sealed to form an insulating space 5 between the electrode 2b and one side of the electrode was coated with a barrier via the insulating space 5 to obtain a single-sided barrier-coated crystal oscillator.

Example 2 An experiment for quantifying odorants and bitter substances in commercially available beer was conducted as follows.

The single-sided barrier-coated crystal oscillator obtained in Example 1 was first immersed in distilled water to determine the frequency, and then immersed in the above beer to adsorb odorants and bitter substances to the immobilized bilayer membrane. When the frequency was measured while immersed, the amount of frequency change due to adsorption was 1800Hz.
The amount of odorants and bitter substances absorbed in proportion to this was 1680 ng.

Comparative Example 1 A fixed bilayer membrane coated crystal oscillator similar to that of Example 1 except that it was not coated with a barrier was measured for frequency while immersed in the beer, but no oscillation occurred and measurement was impossible. Ta.

Example 3 An experiment similar to Example 2 was conducted except that commercially available sake was used instead of beer in Example 2. The frequency change was 1300 Hz, and the odorants and bitterness in the sake were proportional to the change in frequency. The amount of substance adsorbed is 1385ng
Met.

Comparative Example 2 When the frequency was measured in the same manner as in Example 3 except that a crystal oscillator without barrier coating was used, no oscillation occurred and measurement was impossible.

Example 4 A quantitative experiment similar to Example 2 was conducted except that commercially available milk was used instead of beer in Example 2. The frequency change was 2700 Hz, and the odorants in milk and The adsorption amount of bitter substances is 2835n
It was g.

Comparative Example 3 When the frequency was measured in the same manner as in Example 4 except that a crystal oscillator without barrier coating was used, no oscillation occurred and measurement was impossible.

Example 5 An experiment similar to Example 2 was conducted except that polyvinyl chloride, which is a polymer membrane, was used as the adsorption membrane. The frequency change was 4901 (z, which is the amount of adsorption of odorants and bitter substances in beer). was 515 ng.

Comparative Example 4 When the frequency was measured in the same manner as in Example 5 except that a crystal oscillator without barrier coating was used, no oscillation occurred and measurement was impossible.

Example 6 An experiment similar to Example 3 was conducted except that polyvinyl chloride, which is a polymer membrane, was used as the adsorption membrane. The frequency change was 820 Hz, and the amount of adsorbed odorants and bitter substances in Japanese sake was 872 ng. Met.

Comparative Example 5 When the frequency was measured in the same manner as in Example 6 except that a crystal oscillator without barrier coating was used, no oscillation occurred and measurement was impossible.

[Brief explanation of drawings]

FIG. 1 shows the first part of the single-sided barrier coated crystal oscillator of the present invention.
1 is a cross-sectional view showing an aspect of the invention. In FIG. 1, 1 is a crystal plate, 2a and 2b are electrodes, 3a and 3b are adhesives, and 4
is silicone rubber, 5 is insulation space, 6 is plastic plate,
7 is an adsorption film. FIG. 2 shows the second half of the single-sided barrier coated crystal oscillator of the present invention.
2 is a cross-sectional view showing an aspect of the invention. In FIG. 2, 1 is a crystal plate, 2a and 2b are electrodes, 3 is an adhesive, 4 is an insulating space,
5 is a plastic member, and 6 is an adsorption film. FIG.
In FIG. 3, 1 is a crystal plate, 2a and 2b are electrodes, 3 is an insulating space, 4 is a barrier integrally formed with the crystal plate 1, and 5 is an adsorption film.

Claims (1)

[Claims] 1. A method for quantifying substances or ions contained in a non-deionized solution using a crystal oscillator, in which one of both electrodes of the crystal oscillator is brought into substantially close contact with the crystal oscillator. A barrier coating is applied to prevent the non-deionized solution from permeating through a certain insulating space without the need for a barrier coating, and an adsorption membrane is cast on the other electrode, and then one side of both electrodes is coated with the barrier coating and the other side is coated with the adsorption membrane. A crystal oscillator coated with is immersed in the non-deionized solution, and the substances or ions contained in the non-deionized solution are respectively adsorbed or chemically bonded to the adsorption film, and the frequencies before and after the adsorption or chemical bonding are determined. change,
The substance or ion contained in the non-deionized solution is determined by measuring the single-sided barrier-coated crystal oscillator while immersed in the non-deionized solution. method for quantifying substances or ions. 2. A crystal oscillator used in a method for quantifying substances or ions contained in a non-deionized solution, in which one of the two electrodes is connected to the crystal oscillator through a certain insulating space without being in substantial contact with the crystal oscillator. The single-sided barrier-coated crystal oscillator is coated with a barrier so that the non-deionized solution does not pass therethrough, and an adsorption film is cast on the other electrode.