JP2006010317A - Intraoral gas measurement method and insertion gas holder used therein - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an intraoral gas measurement method for accurately measuring intraoral gas in a simple and safe manner, and an insertion gas holder used therefor. <P>SOLUTION: Since an end introduction part 2a of this insertion gas holder 1 is columnar, the holder 1 is inserted into an oral cavity without damaging the interior of the oral cavity, the intraoral gas is caused to adsorb to and be held by an adsorption/desorption part 2 made of adsorption/desorption material having a surface area of 50 cm<SP>2</SP>or more, and then the adsorption/desorption part 2 is conveyed and heated to desorb the intraoral gas. Since a gas chromatography can be used for measuring the constituents of the intraoral gas, the intraoral gas can be accurately measured in a simple and safe manner. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for measuring an intraoral gas and an insertion gas holder used therefor, in which the intraoral gas is simply measured in order to diagnose periodontal disease and analyze odorous gas generated from the oral cavity.

  The main cause of periodontal disease is P.P. G. gingivalis, A. In addition to Actinomycetemcomitans, periodontal tissues are destroyed by infection of the periodontal pocket deeply by several pathogenic anaerobic bacteria. Odorous sulfur compounds such as methyl mercaptan, dimethyl sulfide, and hydrogen sulfide are generated by proteolysis of periodontal tissues and blood components. Since these anaerobic bacteria are carried throughout the body by blood flow and can infect other organs, early treatment of periodontal disease is required, but it is often left unattended because subjective symptoms are difficult to occur. In this case, periodontal disease infection can be examined by a blood antibody test or a saliva bacteria test at a regular health checkup, but this is not generally performed because of the high cost of the test.

  Conventionally, it is known that various diseases and physical conditions can be examined and diagnosed by chemical composition analysis of exhaled breath, for example, liver disease and diabetes are suspected by ammonia and acetone in exhaled breath, respectively. As an example of this, it is known that various diseases can be examined by the content distribution of n-alkane and methylalkane having 4 to 20 carbon atoms in exhaled breath (see, for example, Patent Document 1).

  In addition, it is known that by ingesting urea labeled with isotopes and analyzing carbon dioxide containing isotopes in exhaled breath, it is possible to test for infection of H. pylori causing gastric ulcer. Therefore, various breath collection containers have also been proposed (see, for example, Patent Documents 2 to 4). It is also known that the smell of chemical components contained in exhaled breath is recognized as bad breath and the breath collection container is used for the purpose of breath breath inspection (for example, see Patent Document 5).

  However, in addition to the chemical components that are excreted from the lungs as exhaled air according to the condition of the whole body, bad breath involves the odorous chemical components produced by the above-mentioned oral resident bacteria. Among these, in the sulfur compound gases such as hydrogen sulfide, methyl mercaptan, and dimethyl sulfide described above, the minimum perceived concentrations are 1 ppm, 0.003 ppb, and 0.4 ppm, respectively. In the case of methyl mercaptan having the lowest threshold, the gas concentration in the oral cavity is It is said that bad breath is felt in real life at 0.2 to 0.5 ppm. Since it is difficult to easily and directly measure such a low-concentration gas, a method for estimating the sulfur gas concentration using an amino acid derivative that produces a colored substance by a bacterial enzyme reaction (see, for example, Patent Document 6) A method of measuring the gas produced according to the number of bacteria after rinsing the mouth with a certain drug (see, for example, Patent Document 7) has been proposed. Since these methods are somewhat complicated and not direct measurement, they have not been widely adopted.

  For this reason, various breath odor measuring devices and periodontal disease diagnosis devices that collect gas in the oral cavity have been conventionally known (see, for example, Patent Documents 8 and 9), and oral gas is sucked with a syringe (without an injection needle). There are commercially available devices for collecting and measuring directly from a syringe into a device with a sensor after collection, and devices for inserting and measuring a sensor in the oral cavity. However, these devices are used for determination by bringing the device itself into the intraoral gas collection site, and have not yet been widely used in health examinations. A simple device based on gas chromatography is also available on the market, but it is convenient for measurement at a dental clinic, but it is a method of directly injecting oral gas collected with a syringe into the device. Sometimes it is necessary to bring a large number of devices to the site, and there are practical difficulties. Although there is a method of using a test paper or a detection tube for measuring gas in the oral cavity, no practical method has been found for direct measurement of gas in the oral cavity due to measurement sensitivity and accuracy.

  A method for measuring chemical components and concentrations of gas mixtures by gas chromatography is generally established, and measurement of gas components in the oral cavity by gas chromatography is characterized by separating sulfur gas and quantifying each component. By measuring the type and amount of gas, it is possible to distinguish between bad breath caused by tissue destruction due to periodontal disease and bad breath generated by microorganisms adhering to tongue coating, and to diagnose periodontal disease.

  On the other hand, there is also known a method of measuring the chemical component concentration in a solution by measuring the chemical component concentration in a gas in equilibrium with the solution. Conventionally, for measuring trace odorous organic sulfur compounds in wastewater, the wastewater is brought into contact with an easily volatile organic solvent that does not mix with water, the sulfur compound is extracted into an organic solvent, the organic solvent is evaporated, and the sulfur compound is concentrated. In general, the measurement is performed by gas chromatography using a method, but recently, the headspace solid-phase extraction method has begun to be employed (for example, Patent Document 10).

In the headspace solid phase extraction method, the concentration of odorous organic sulfur compounds in the sealed air portion (headspace) in which wastewater is taken in a bottle is in constant equilibrium with the concentration of each sulfur compound in the wastewater. A single fiber with a diameter of about 0.1 mm can adsorb an equilibrium amount of sulfur compound proportional to the concentration of each sulfur compound in the headspace, and the fiber is drawn into the injection needle and introduced directly into the gas chromatography vaporization chamber. Therefore, the measurement principle is that the measured value of each sulfur compound is proportional to the concentration of each sulfur compound in the wastewater. When the chemical activity of the adsorbent is high, the substance to be desorbed in the gas chromatography may have undergone a certain chemical change, but the concentration of the gas in the headspace or the concentration of odorous compounds in the wastewater and the substance concentration to be desorbed. If there is a certain correlation between them and a calibration curve can be drawn, this method can be used effectively. However, one special fiber housed in the injection needle of this method is intended to be repeatedly used for various measuring objects and is expensive. Adsorption (solid phase extraction) and gas chromatography measurement are performed at the same place. Therefore, it is not suitable to use a large number of injection needles and fiber sets, or to transport after adsorption.
JP-T-2002-534697 JP-A-8-304394 JP-A-9-105721 JP 2002-257695 A JP 2001-108582 A JP-A-4-299998 JP-A-8-224239 JP 2002-286670 A Japanese Patent Application Laid-Open No. 2002-255354 US Pat. No. 5,691,206

  In collecting and measuring oral gas, it is conceivable to use the solid-phase extraction method due to its special characteristics such as trace amount and low concentration, but conventionally, oral gas can be measured by gas chromatography in the oral cavity. Thus, it was not carried out at all by direct adsorption. If a conventional needle-type needle that pulls in the fiber, which is a suction type, is put into the mouth and collected, the ultra-thin fiber may break when touching the cheek or tongue, and the needle-like shape when inserted Can pierce the inside of the oral cavity and cause damage, and is difficult to use by non-professionals such as dentists.

Despite the fact that periodontal disease and the presence of odorous gas generated in the oral cavity have a significant impact on health and social life as described above, the person himself is unaware of the progression of his / her condition and is related to shame. It is difficult to point out people around you. On the other hand, since it has not been possible to perform tests for periodontal diseases caused by gas in the oral cavity easily and at low cost, the generalization of tests such as the implementation at the time of a health check has been hindered. Therefore, if oral gas can be held easily, it will lead to early diagnosis by objective data obtained by measuring oral gas using a gas separation measuring device such as gas chromatography installed separately from the oral gas collection location. Since quantitative analysis can be performed, there has been a demand for a method for measuring oral gas that can be separately measured by holding such oral gas and an insertion gas holder used therefor. The present inventor considered collecting and transporting oral gas into a gas barrier bag, but about 150 ml of model gas containing 5 ppm hydrogen sulfide, 5 ppm methyl mercaptan, and 1 ppm dimethyl sulfide in a bag having a surface area of about 400 cm ^2. When trying to collect and store, sulfur compounds adsorbed on the inner surface of the bag immediately after collection, and it was found that the concentration decreased rapidly and significantly.

  The present invention has been made in view of the above problems, and an object thereof is to provide a method for measuring an intraoral gas capable of accurately measuring an intraoral gas easily and safely, and an insertion gas holder used therefor. Yes.

  As a result of various examinations of separation, measurement, and quantification methods of odorous sulfur compounds in oral gas by gas chromatography, the present inventor collects oral gas in a collection container because the measurement target is a small amount and low concentration. This is because the oral gas is affected by adsorption to the container, the moisture in the oral cavity is high and moisture is condensed in the container, and it is easily affected. Although it is difficult because of problems such as adsorption, a method has been devised to reliably measure trace components by actively utilizing this adsorption phenomenon, which makes analysis of trace components difficult. .

  In this method, the gas concentration is measured by using an adsorbent by utilizing the situation and peculiarity of the intraoral gas to be measured. That is, the suction tool to be inserted into the oral cavity is used with a large surface area in order to ensure safety first and then to secure adsorption performance. In the case of measurement of gas in the oral cavity, the adsorbent does not necessarily have to be in an adsorption equilibrium state with the gas in the oral cavity, the adsorption conditions are constant at 37 ° C., and the humidity is constant at 100%. The time during which the oral cavity is held in the oral cavity can also be set constant, for example, 5 minutes. This may be due to the fact that the amount of adsorption in proportion to the concentration of gas in the oral cavity is ensured safely and easily even when using certain columnar adsorbents that have not been practical for a long time until they reach adsorption equilibrium in general use. The adsorbent is introduced into the sample introduction part of the gas chromatography and the adsorbent is desorbed by raising the temperature, or the adsorbent is placed in a sealed container of a certain size and the adsorbent is desorbed by raising the temperature. It was found that the concentration of intraoral gas can be calculated by a simple calibration curve by introducing a certain portion of the gas into a gas chromatography and measuring the amount of each desorbed substance, thereby completing the present invention.

The amount of adsorption of the measurement target substance in the oral cavity gas to the adsorption / desorption material, and therefore the desorption amount, increases as the surface area of the adsorption / desorption material increases, and the measurement accuracy increases as this increases. On the other hand, in recent years, the measurement sensitivity and accuracy of gas chromatography have been remarkably improved, so that even an adsorption / desorption material having a small surface area can be measured. Also in the measurement of trace components of gas in the oral cavity which is the object of the present invention, the required analysis accuracy was obtained if the surface area of the adsorption / desorption material was 50 cm ² or more. That is, the method for measuring intraoral gas according to the present invention includes a columnar insertion having an adsorbing / desorbing portion made of an adsorbing / desorbing material with a surface area of 50 cm ² or more having a non-pointed columnar tip introducing portion for safety. A gas holder is inserted into the oral cavity from the tip introduction part, and the oral gas is adsorbed and held in the adsorption / desorption part for a certain period of time (for example, 5 minutes), preferably the adsorption / desorption part is sealed, It conveys to an installation place, the said adsorption | suction / desorption part is heated, at least a fixed part of the adsorbed intraoral gas is desorbed, and an intraoral gas component is measured by gas chromatography.

  According to this configuration, since the distal end introduction portion of the insertion gas holder is columnar, the insertion gas holder is inserted into the oral cavity without damaging the oral cavity, and the oral gas is adsorbed and held in the adsorption / desorption portion. be able to. In measurement, it is possible to measure by desorbing the measurement target substance from the adsorption / desorption part by attaching the adsorption / desorption part to the sample injection part of the gas chromatography via the tip introduction part of the insertion gas holder, Easy and safe measurement of gas in the oral cavity. In addition, it is more preferable that there is no extra volume at the place where desorption is performed because the concentration of the desorption gas can be increased.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. FIG. 1 is a configuration diagram showing an insertion gas holder used in a method for measuring gas in the oral cavity according to an embodiment of the present invention. The insertion gas holder 1 includes an adsorption / desorption portion 2 made of an adsorption / desorption material having a columnar tip introduction portion 2a such as a rod, and a grip portion 3 held by an operator. The adsorption / desorption unit 2 has a predetermined gas adsorption area in order to ensure quantitativeness of analysis by gas chromatography described later. The insertion gas holder 1 is hermetically housed and transported by a portable case 7 including an elongated bottomed container 5 and its lid 6. The inner surface of the portable case 7 is formed of a material having a low gas adsorbability.

  The insertion gas holder 1 is inserted into the oral cavity from the tip introduction part 2a, and is held in the oral cavity for a certain period of time (for example, 5 minutes) in a state where the oral cavity and the outside are hermetically blocked by the lips. Then, the intraoral gas is adsorbed and held by the adsorption / desorption part 2. After the intraoral gas is adsorbed, the insertion gas holder 1 is hermetically stored in the portable case 7 and temporarily stored. Thereafter, the inserted gas holder 1 is usually transported to a gas chromatography installed in a place away from the place of implementation while being housed in the portable case 7.

  At the place where the gas chromatography is installed, the insertion gas holder 1 is taken out from the portable case 7 and its adsorption / desorption part 2 is put into the sample injection part of the gas chromatography, and the component to be measured is desorbed from the adsorbent by raising the temperature. Then, it is measured by a conventional gas chromatography measurement method. In order to insert the insertion gas holder 1 that has adsorbed the gas to be measured into the gas chromatography sample injection part, there is a method in which the adsorption / desorption part 2 is directly inserted into the sample injection part via the tip introduction part 2a through a rubber plug or the like. Conveniently, the adsorption / desorption unit 2 or the insertion gas holder 1 is housed in an open / close type sample receiving chamber connected to the sample injection unit, the measurement target gas is released by heating, and the sample is injected using the carrier gas. It is also possible to send it to the section. Also, only the adsorbing / desorbing material in the adsorbing / desorbing section 2 is directly placed in the sample receiving chamber or sealed in a vial, and the vial is heated for gas chromatography measurement using an existing autosampler, and the oral cavity is A gas-related component can be desorbed, and a gas portion containing the desorbed component can be collected and measured by a conventional method from a vial.

The adsorption / desorption part 2 of the insertion gas holder 1 is columnar, for example, like a toothpick so that it can be easily inserted into the oral cavity sealed with lips and can be easily inserted into the sample injection part of gas chromatography. (Bar shape), that is, it is convenient that the tip introduction portion 2a has a thin rod shape and the subsequent portion has a slightly thicker rod shape. The cross-sectional shape of the adsorption / desorption part 2 is not particularly limited, but is preferably circular or elliptical. In the case of a circular shape, the diameter is 8 mm to 0.5 mm (cross-sectional area 50 mm ² to 0.2 mm ² ), preferably about 8 mm to 1 mm in diameter (cross-sectional area 50 mm ² to 0.8 mm ² ). It is suitable in terms of sealing property by the lips and insertion property to the sample injection part.

  The materials of the adsorbing / desorbing part 2 and the gripping part 3 of the insertion gas holder 1 may be chemically the same or different, and the cross-sectional shapes of both may be different. Good. Further, any method for combining the two may be used.

  From the viewpoint of ease of insertion into the oral cavity, the insertion gas holder 1 has a length of the adsorbing / desorbing part 2 to be inserted into the oral cavity of 1 cm to 10 cm, preferably 1 cm to 5 cm. The total length of the tool 1 is not particularly limited. On the other hand, in order to ensure the quantitative property in gas chromatography, the adsorbing / desorbing material inserted into the oral cavity, directly inserted into the gas chromatography sample injection part, or stored in the sample receiving chamber has a fixed length of about 1 cm to 3 cm. It is desirable to be. For this reason, it is preferable to mark the insertion gas holder 1 with a certain length, or to provide a protruding portion in the insertion gas holder 1 or to change its thickness in order to limit insertion into the gas chromatography sample injection part. .

  The adsorption / desorption material having a large specific surface area may be either an inorganic substance or an organic substance. Typical high surface area materials include porous materials, fine powders, ultrafine fibers, and ultrathin films. The insertion gas holder having a large specific surface area may be a porous material having a large number of pores, a fine powder compressed and bonded, a microfiber, or a nanofiber compressed and bonded. The material is not particularly selected as long as it does not form a strong reaction product with the gas to be measured. Typical materials include carbon materials, calcium phosphate materials such as silica, alumina, zeolite, silicate glass, hydroxyapatite, metal materials, Teflon (registered trademark), polysulfone, polyarylate, styrene divinylbenzene copolymer, etc. Can do. In addition, general polymer materials such as polyethylene terephthalate, polyamide, polypropylene, and polyvinyl alcohol can also be used. Further, by covering the adsorption / desorption part 2 with a porous hydrophobic resin film, wetting by saliva and fluctuations in adsorption conditions can be prevented. Examples of suitable porous hydrophobic resins include expanded fluororesin films and expanded polyolefin films. Covering the adsorption / desorption part 2 with a hydrophobic porous hollow fiber membrane or a porous tube membrane is a preferred embodiment.

The adsorption / desorption material of the adsorption / desorption part 2 of the present invention can be used for measurement if the surface area is 50 cm ² or more. If the surface area is 100 cm ² or more, more preferably 1000 cm ² or more, the measurement accuracy is improved, which is more preferable. In order to increase the surface area with a certain size, the adsorbing / desorbing material preferably has a large specific surface area. For this reason, a preferable adsorption / desorption material has a specific surface area of 1 m ² / g or more, and if the specific surface area is 10 m ² / g or more, the adsorption amount of the measurement target gas is large, which is preferably used. Silica gel or a specific surface area of several 100 m ² / g, may be used specific surface area of 1000 m ² / g or more activated carbon. Further, an organic polymer having a specific surface area of about 100 m ² / g such as wet coagulated hollow fiber used as a separation membrane may be used. Fibers, non-woven fabrics, etc., or processed products are preferred materials with a large specific surface area. The finer the surface area, the smaller the specific surface area of microfibers, nanofibers, etc. Nonwoven fabrics and processed products are the most preferred materials. Textile products are characterized by a high rate of adsorption and desorption. Here, the surface area means that obtained as a calculated value from the specific surface area obtained by the nitrogen adsorption BET method.

  The surface of a material having a large specific surface area can be thinly coated with a polymer to increase the amount and speed of extraction by the material and desorption in the gas chromatography sample injection part. For the purposes of the present invention, coating with polydimethylsiloxane, polyethylene glycol, polypropylene glycol, polyacrylate, and the like can be performed.

  In the present invention, it is preferable in terms of hygiene that the insertion gas holder having a large specific surface area such as a porous material should be disposable only once.

  When the adsorption / desorption part 2 having a large surface area is inserted into the oral cavity, if the adsorption / desorption part 2 is wetted by saliva, the conditions for adsorbing the gas in the oral cavity vary, making it difficult to ensure quantitativeness. For this reason, as shown in the modification of FIG. 2 (A), it is a more preferable embodiment to cover the adsorption / desorption portion 2 with a porous cover 14 provided with a large number of holes. The porous cover 14 is preferably made of a hydrophobic resin.

  Although the adsorption speed of the adsorption / desorption part 2 is slowed by the porous cover 14 on the surface, the adsorption and desorption speed can be increased by thinning the adsorbent material, and the quantitativeness by gas chromatography can be improved. In addition, it is effective to use a material for the adsorption / desorption portion 2 in the porous cover 14 as an adsorption / desorption material having a larger specific surface area.

  2A is fitted and fixed to the porous cover 14 at a thin portion 15c, and has a shape with a step 15d to form a part of a portable case. When the suction / desorption portion 2 is accommodated together with the porous cover 14 in the elongated bottomed container (portable case) 16, the tip portion 16a abuts on the step 15d, and the outer surface of the portion 14b of the porous cover 14 where there is no hole. The inner surface of the bottomed container 16 is closely contacted to seal the inside. The porous cover 14 is provided with an adsorption / desorption portion 2 made of an adsorption / desorption material having a large surface area, but the adsorption / desorption portion 2 may be fixed to the grip portion 15 or free. As an example, as shown in FIG. 2C, a film, paper, cloth (nonwoven fabric) 12, or fiber is put as the adsorption / desorption material of the adsorption / desorption portion 2. The fiber may be cotton-like or may be a fiber cut to a certain length. As shown in FIG. 2D, a fiber 22 wound around a frame 24 is preferable because the gas adsorption and desorption speed can be controlled. Also, it is convenient to fix the fibers to the holding material in a brush shape and to form a columnar shape. In particular, as shown in FIG. 2 (E), the fibers 32 are fixed to the wire 36 in an interdental brush shape. Inserting and fixing to the distal end side of the gripping portion 15 in (A) can fix a large amount of fibers with high adsorption efficiency, and is also convenient for insertion into gas chromatography. Porous rod-like or sheet-like materials made of a wet solidified polymer material or a film can also be suitably used in terms of the balance of production, handleability, adsorption, and desorption characteristics.

  In the modification of FIG. 2, when measuring the gas in the oral cavity, the adsorption / desorption part 2 whose surface is covered with the porous cover 14 is held in the oral cavity for a certain period of time, for example, 5 minutes. After making it adsorb | suck to desorption material, the portable case 16 is covered from on the porous cover 14, and is sealed and accommodated. When the adsorbing / desorbing material is fixed to the gripping part 15, the porous cover 14 may be removed and the adsorbing / desorbing part 2 may be directly stored in the portable case 16. In this state, the sample is transported to an analysis center where gas chromatography measurement is performed and used for analysis. In the analysis, the portable case 16 is removed, the adsorption / desorption part 2 covered with the porous cover 14 is put into the sample introduction part of the gas chromatography, and the heated and desorbed gas is guided to the column by the carrier gas introduced into the loop. The adsorbing / desorbing material is directly inserted into the sample injection part via the tip introduction part 2a of the porous cover 14, or the adsorbing / desorbing material is sealed in a vial, and the gas adsorbed by the temperature rise is desorbed, headspace gas Can be introduced into the column by an autosampler according to a conventional method, and oral gas can be separated and quantified for each chemical component. By using a flame photometric detector or a chemiluminescent sulfur detector, sulfur-containing compounds can be analyzed with high accuracy.

The porous cover 14, the gripping part 15, and the transportable case 16 are preferably made of a smooth material with little absorption of intraoral gas. Suitable materials from the standpoint of adsorptivity and moldability include liquid crystal polymers such as Vectran and polypropylene. When the surface area is large as an adsorbing / desorbing material, competitive adsorption on the surface of a smooth material is not a big problem when a material of 100 cm ² or more, particularly, paper, cloth or fiber of 1000 cm ² or more is used. However, in order to prevent and minimize the dissolution and diffusion of the substance to be measured inside the porous cover 14, the gripping part 15, and the portable case 16, the number of days until the gas chromatography measurement is shortened after the oral gas is adsorbed. It is preferable. Although the moldability is difficult for the purpose of preventing dissolution and diffusion of the substance to be measured, inorganic materials, particularly glass, are suitable.

Paper, cloth (nonwoven fabric), cotton, and fiber having a specific surface area of 1 m ² / g or more, particularly preferably 100 m ² / g or more, are produced with nanofibers such as activated carbon fiber, porous silica fiber, polyester, nylon, or polypropylene. can do. Nanofibers such as silicon oxide and silicon nitride are also included.

The porous cover 14 has a length of 1 cm to 10 cm, preferably 1 cm to 5 cm, as described above with respect to the adsorption / desorption part 2, and has a cross section from the outer surface of 50 mm because of its sealing property by lips and ease of introduction into gas chromatography. ² to 1 mm ² is preferred. The total length of the perforated cover 14 containing the adsorbing / desorbing material and the grip portion 3 is, for example, 15 cm. It is convenient to manufacture the porous cover 14 by injection molding. In this case, it is general that the tip portion is thin and the portion joined to the grip portion 3 is thick. 1 and 2, the adsorption / desorption part 2 and the gripping part 3 are linear rods, but the gripping part 3 may be bent or bent so as not to be inconvenient for insertion into the oral cavity.

Hereinafter, the present invention will be described specifically by way of examples. In addition, this invention does not receive any limitation by this.
Example 1
Diameter 1mm, length 20 mm, the porous hydroxyapatite cylinder inner diameter 1mm surface area 470 cm ^2, an outer diameter of 2 mm, slightly inserted and fixed polypropylene tubing end length 10 cm, inserting a gas holder for suction holding buccal gas It was created. As a model of oral gas containing odorous sulfur compounds, a standard gas containing 4.9 ppm hydrogen sulfide, 4.8 ppm methyl mercaptan, and 0.9 ppm dimethyl sulfide is generated by a permeator (calibration gas regulator), and the capacity is 1 While maintaining the standard gas in a liter odor bag, a 1/2 dilution gas, a 1/5 dilution gas, and a 1/10 dilution gas were prepared. The adsorption / desorption part 2 of the insertion gas holder for adsorbing and holding oral gas was inserted into these odor bags and held at room temperature for 5 minutes. The insertion gas holder was taken out from the odor bag, the porous hydroxyapatite cylindrical portion was removed, placed in a glass bottle with a capacity of 50 ml, sealed with a butyl rubber stopper, and stored for 1 day. Then, using gas chromatography (GC-17A, manufactured by Shimadzu Corporation), an apatite cylinder was placed in a temperature rising sample injection unit, the temperature was raised to 200 ° C., and the desorption sample gas was transferred to a GC-Q, 0.53 mm, 30 m column. After introduction, the temperature was raised at 10 ° C./min, 60 to 250 ° C., and analyzed with a flame light type detector. The peak height according to the separation and dilution of each component of the model gas of the oral gas could be measured. A standard curve was created with the peak height of the 1/5 dilution gas and 1/10 dilution gas, and the gas concentration of the 1/2 dilution gas was calculated. It became 2.3 ppm for mercaptan and 0.4 ppm for dimethyl sulfide, indicating that the insertion gas holder having this porous hydroxyapatite cylinder can be used for measuring the concentration of odorous sulfur compound gas.

Example 2
The length of the needle cover is 5mm to 4mm, the inner diameter is 5mm to 4mm, the length is 3.5cm, and the outer diameter is 5mm and 6mm. A 4 cm long grip was created. A portable case was also made of polypropylene in the same manner. An activated carbon fiber non-woven fabric piece having a specific surface area of about 500 m ² / g as an adsorbent was put into this porous cover to form an adsorbing / desorbing section, and a gripping section was inserted to prepare a rod-shaped insertion gas holder. The adsorption / desorption part containing the adsorbent of the insertion gas holder was inserted into the odor bag containing the intraoral gas model gas described in Example 1, and held for 10 minutes. The adsorption / desorption part containing the adsorbent was sealed with a transportable case and stored for one week. After 1 week, the adsorbent was transferred to a glass sample bottle, sealed, heated to 150 ° C. on a turntable, and headspace gas was injected into the gas chromatograph according to a conventional method to analyze sulfur-containing compounds.

Example 3
A wire brush (fiber weight 2 mg, surface area) with a 10 cm denier yarn aggregate with a specific surface area of 50 m ² / g, a total length of 3 cm as a material for adsorbing and desorbing oral gas, a brush part of 1.5 cm, and a hair length of 1 mm 1000 cm ² ). Insert a portion of 1.5 cm with no hair into the hole formed in the grip part of Example 2 by about 0.5 cm, and combine it with a 3.5 cm long porous cover of Example 2 and a transportable case. An insertion gas holder used for adsorption, transportation and desorption was prepared.

It is a block diagram which shows the insertion gas holder used for the measuring method of the intraoral gas which concerns on one Embodiment of this invention. It is a block diagram which shows the modification of the insertion gas holder of the embodiment.

Explanation of symbols

1: Insertion gas holder 2a: Tip introduction part 2: Adsorption / desorption part 7: Transportable case 14: Porous cover 16: Transportable case

Claims (4)

A columnar insertion gas holding tool having a columnar tip introduction portion and having an adsorption / desorption portion made of an adsorption / desorption material having a surface area of 50 cm ² or more is inserted into the oral cavity via the tip introduction portion, and the oral gas is introduced. The adsorbing / desorbing part is adsorbed and held and then transported, the adsorbing / desorbing part is heated to desorb oral gas, and the gas component in the oral cavity is measured by gas chromatography, Measuring method. Wherein the adsorption and desorption portions of the cross-sectional area of 50mm ² ~0.2mm ^2, a length of 1Cm～10cm, measurement method of intraoral gas according to claim 1.   The insertion gas holder is stored in a portable case that hermetically stores at least the adsorption / desorption portion until the intraoral gas is desorbed during gas chromatography measurement after the intraoral gas is adsorbed and held. 2. The method for measuring gas in the oral cavity according to 2. 4. Adsorption / desorption with a surface area of 50 cm ² or more by a porous cover having a columnar tip introduction part and a large number of holes in the body part, which is used in the method for measuring gas in the oral cavity according to claim 1. A disposable (one-time use) insertion gas holder in which the adsorption / desorption portion made of a material is covered.

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