JP2012058065A - Imaging device for odor distribution - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an imaging device for odor distribution for visualizing the distribution of odor.SOLUTION: The imaging device for odor distribution includes: an adsorption sheet having an adsorption surface of odor substances; an excitation light source for radiating excitation light to the adsorption sheet; an image pickup apparatus for fluorescence on the adsorption sheet; and a display device for displaying a change amount of fluorescence intensity distribution as image data. The adsorption sheet is provided with adsorption materials containing fluorescence dye whose prescribed wavelength fluorescence changes by adsorbing prescribed odor substances, in a layer. By adsorbing odor substances, light emission intensity of the fluorescence is reduced. For example, the fluorescent dye includes acridine orange, fluorescein, pyrene, allylnaphthalene sulfonic acid, tryptophan, quinine sulfate, fluorescent peptide, and quantum dot ZiSe. The adsorption sheet may mix, adsorb, or blot the fluorescent dye in a group of polymeric beads having 10 nm to 100 μm and level them in a sheet shape.

Description

  In this invention, the spatial distribution of odors (odors and odors) is fixed on a plane or a three-dimensionally arranged plane, and converted to a fluorescence distribution of wavelengths that can be imaged by an imaging device by irradiating excitation light. The present invention relates to an odor distribution imaging device that visualizes the image.

  In recent years, there is a need for a method that can objectively evaluate the quality and quantity of odors for solving problems such as bad odor pollution, gas explosions, poisoning, and more comfortable living. There are several sensors that can measure odor.

  Various odor sensors are known. For example, an odor molecule is adsorbed by attaching a molecule-selective receptor to the vibrator, and the odor molecule is detected by a change in its frequency, or the resistance value can be changed by using a hot-wire sintered semiconductor element. A device to be detected or a device using an ISFET (ion-sensitive field effect transistor) in which an adsorption layer for adsorbing an odor substance is provided on a gate film is already on the market.

  As an ultra-sensitive odor sensor, an antigen-antibody reaction type surface plasmon resonance sensor is known. This sensor is composed of an antibody that selectively recognizes a target by an antigen-antibody reaction that occurs on the gold surface, and a surface plasmon resonance (SPR) detector that converts the concentration of the target into an electrical signal.

  Further, an integrated multi-channel odor sensor is known as having a planar sensor head. This is an odor code sensor that recognizes odors into several subsets.

  Moreover, although it is a measuring apparatus of nitric oxide, as an apparatus which measures fluorescence, there exists a measuring apparatus of nitric oxide etc. which were described in patent document 1 (Unexamined-Japanese-Patent No. 2010-78426). In this patent document, a sample gas containing nitric oxide (NO) and a gas absorbing solution containing a NO fluorescent probe are brought into contact with each other through a gas permeable membrane, and nitrogen monoxide is taken into the gas absorbing solution. A method for measuring nitric oxide comprising measuring the amount of fluorescence in an absorbing solution is disclosed. Further, a gas flow path through which a sample gas containing nitric oxide flows, a gas absorption liquid flow path through which a gas absorption liquid containing NO fluorescent probe flows, and a boundary surface between the contact portions of the gas flow path and the gas absorption liquid flow path A nitrogen monoxide measuring device is disclosed in which a gas collector provided with a gas permeable membrane and a fluorescence detector provided in a gas absorption liquid outlet side channel of the gas collector are disclosed.

  Further, an odor sensor that detects the fluorescence of an odor substance attached to a membrane-like receptor is described in Patent Document 2 (Japanese Patent Laid-Open No. 9-189663). In this method, a film of phthalocyanines is excited and irradiated to measure the fluorescence intensity.

  However, the problem of non-specific adsorption that responds to substances other than the substance to be measured remains in existing sensors. In view of this, the present invention proposes an odor sensing device that can solve this non-specific adsorption problem. As the technique, the present invention uses fluorescence. In general, odorous substances are believed to interact with fluorescent dyes and directly affect fluorescence. In the present invention, the odorous substance is detected by using the fluorescent dye as a site for accepting the odorous substance and taking out the interaction between the fluorescent dye and the odorous substance as a change in fluorescence.

JP 2010-78426 A JP-A-9-189663

  In general, it is possible to detect an odorous substance by fluorescence analysis using a fluorescent dye, that is, to detect an odor as a change in fluorescence. However, in the fluorescence measurement using a liquid fluorescent dye, it is difficult to actually measure the odor which is a trace amount of gas.

  An object of the present invention is to realize an odor distribution imaging apparatus that can visualize the odor distribution in this way.

  In general, the present invention uses a fluorescent material formed in a sheet shape, irradiates excitation light, takes an image by a high-sensitivity imaging device, and visually detects the smell and spread of the smell. is there.

  More specifically, the present invention relates to an odor imaging apparatus for imaging an odor substance distribution, an adsorption sheet having an adsorption surface for adsorbing an odor substance, and excitation light for irradiating the adsorption sheet with excitation light. A light source; an imaging device that images fluorescence intensity distribution on the adsorption sheet by the excitation light; and a display device that displays the amount of change in fluorescence intensity distribution from the imaging device as image data. . The adsorbing sheet is provided with an adsorbing material containing a fluorescent dye that changes the fluorescence of a predetermined wavelength by adsorbing a predetermined odor substance in a layer form.

  In particular, the adsorbing sheet reduces the fluorescence emission intensity by adsorbing the odorous substance.

  The adsorbing sheet is obtained by applying or impregnating the adsorbing material to a cloth or paper-like porous material that is stretched on the surface of a flat plate that transmits the excitation light and does not emit fluorescence in the fluorescence wavelength band. is there.

  Moreover, the said adsorption sheet consists of several area | regions, and each area | region contains each fluorescent dye which emits the fluorescence of a different wavelength, when receiving the irradiation of the same excitation light.

  The fluorescent dye is any one of acridine orange, fluorescein, pyrene, allyl naphthalene sulfonic acid, tryptophan, quinine sulfate, fluorescent peptide, and quantum dot ZiSe.

  In addition, after the odor substance is adsorbed on the adsorbing sheet, an adsorption inhibiting layer that inhibits further adsorption is formed. This prevents excessive adsorption during movement.

  The adsorbing sheet is detachable from the odor distribution imaging device. When the odor substance is adsorbed on the adsorbing sheet, the adsorption sheet is separated from the odor distribution imaging device and irradiated with the excitation light. In this case, it is attached to the imaging device having the odor distribution.

  The adsorbing sheet is obtained by applying or impregnating a cloth or paper-like sheet on an acrylic plate with a mixture of a fluorescent dye solution and glycerin or a water-soluble polymer.

  As the adsorption sheet, a quinine sulfate solution in which water and a glycerin aqueous solution are used as a solvent is adsorbed on an acrylic plate, and the time change of the fluorescence intensity distribution is displayed on the display device.

  The adsorbing sheet is obtained by mixing, adsorbing, or soaking a fluorescent dye into a group of polymer beads having a diameter of 10 nm to 100 μm and leveling the sheet. This makes it possible to easily make a multifunctional adsorption sheet by mixing polymer beads using various fluorescent dyes.

  By applying the present invention, the odor distribution can be visualized.

It is a figure which shows the structure of the imaging apparatus of the odor distribution of this invention. In this imaging apparatus, an odor is adsorbed on the adsorption sheet 1. At the time of this suction, the suction sheet 1 is temporarily installed in a place where the odor distribution outside the dark box 5 is to be imaged, and is returned to the place shown in the figure when the suction work is completed. The suction sheet 1 is irradiated with excitation light (for example, light having a wavelength of 254 nm) from the excitation light source 4. By this irradiation, the adsorbing sheet emits fluorescence. This fluorescence is passed through the filter 2 which is a low-pass filter, and the excitation light is blocked. The filtered fluorescence is picked up by an image pickup device 3 such as a cooled CCD camera, and if necessary, data processing for image modification such as superposition and averaging of the picked-up images is performed and displayed on the display device 6. To do. In the configuration of this figure, the suction sheet 1, the excitation light source 4, and the imaging device 3 are housed in a dark box 5. The imaging device 3 and the suction sheet 1 are arranged in parallel, and excitation light is applied to the suction sheet 1 from below. The imaging device 3 is desirably high sensitivity and low noise, and is preferably a cooled CCD camera, for example. Acridine Orange, Fluorescein, Pyrene, Quinine Sulfate, Tryptophan, Tryptophan, the odor substance Furaldehyde vanillin ( It is a figure which shows the quenching rate with respect to Vanilin), benzene (Benzene), and NPOE (Nitrophenyl Octyl Ether). It is a figure which shows the wavelength dependence of the quenching rate at the time of furaldehyde adsorb | sucking to a quinine sulfate (Quinine Sulfate). It is the figure which took time and the brightness | luminance on the vertical axis | shaft in the odor response image at the time of using a quinine sulfate (100 micromol) as a fluorescent pigment | dye and furaldehyde as an odor substance. This figure shows the odor response characteristics of the suction sheet when the odor is sprayed using a pump. It can be seen that when the odor is applied for 30 to 70 seconds, the luminance changes immediately after the odor is applied. (A) shows the schematic diagram of arrangement | positioning of smell shape imaging | photography, (b) shows the example of the obtained smell shape image. (A) shows the schematic diagram of the arrangement | positioning for obtaining an odor distribution image, (b) shows the example of the obtained odor distribution image.

  Embodiments of the present invention will be described below in detail with reference to the drawings. In the following description, devices having the same function or similar functions are denoted by the same reference numerals unless there is a special reason.

  FIG. 1 shows the configuration of an odor distribution imaging apparatus according to the present invention. In this imaging apparatus, an odor is adsorbed on the adsorption sheet 1. At the time of this suction, the suction sheet 1 is temporarily installed in a place where the odor distribution outside the dark box 5 is to be imaged, and is returned to the place shown in FIG. 1 when the suction work is completed. The suction sheet 1 is irradiated with excitation light (for example, light having a wavelength of 254 nm) from the excitation light source 4. By this irradiation, the adsorbing sheet emits fluorescence. This fluorescence is passed through the filter 2 which is a low-pass filter, and the excitation light is blocked. The filtered fluorescence is picked up by the image pickup device 3 such as a cooled CCD camera, and is displayed on the display device 6 by performing data processing for image modification such as superposition and averaging of the picked-up images as necessary. To do. In the configuration of FIG. 1, the suction sheet 1, the excitation light source 4, and the imaging device 3 are housed in a dark box 5. The imaging device 3 and the suction sheet 1 are arranged in parallel, and excitation light is applied to the suction sheet 1 from below. The imaging device 3 is desirably high sensitivity and low noise, and is desirably a cooled CCD camera.

  Further, in the configuration shown in FIG. 1, an image can be taken while flowing the odor by passing a tube through which the odor is poured from the outside, and the time change of the odor response can be observed.

  For the adsorption sheet 1, for example, quinine sulfate (100 μM) that is stable and easily excited by the excitation light source 4 (254 nm) was used. In particular, when measurement is performed by adsorbing on an acrylic plate, a quinine sulfate solution using water as an adsorbing material and a glycerin aqueous solution as a solvent can be used. Further, as an odorous substance used as a test, furaldehyde which responded well to quinine sulfate and acetic acid which is a general odorous substance can be used.

  The odor distribution is imaged as follows. First, a fluorescence image is acquired in a state where excitation light is irradiated using the imaging device 3. Thereafter, the odor is adsorbed on the adsorbing sheet 1 and the fluorescence image is taken again in a state where the excitation light is irradiated. By subtracting or dividing the difference between before and after odor adsorption, the portion where the odor is adsorbed appears on the display device 6. Thus, the smell can be detected from the change in luminance. Moreover, although it is roughly, the shape of an odor can be acquired from a display image.

  The adsorbing sheet 1 is placed in a position very close to the surface where the odor is adsorbed or in a space where the odor is distributed, and the odor substance is adsorbed to change the fluorescence of the fluorescent dye. In the case of a small amount of odor, many odors are adsorbed by standing for a long time. FIG. 5 shows an example of using this to photograph the shape of the odor distribution. FIG. 5A shows the positional relationship between the odorous substance and the adsorption sheet. The obtained image is shown in FIG. Looking at the difference image, it can be seen that the shape of the odor distribution is reproduced.

  By taking images at regular intervals, it is possible to capture temporal changes in odor. For example, when an odor substance is applied to the adsorption sheet 1 using a pump, only the portion where the odor substance is sprayed emerges, and the spatial distribution of the odor is known. In addition, it is possible to capture temporal changes in the odor distribution by taking images at regular intervals. FIG. 4 shows an odor response image when quinine sulfate (100 μM) is used as a fluorescent dye and furaldehyde is used as an odor substance, with time on the horizontal axis and luminance on the vertical axis. FIG. 4 shows the odor response characteristics of the suction sheet when the odor is sprayed using a pump. It can be seen that when the odor is applied for 30 to 70 seconds, the luminance changes immediately after the odor is applied.

  FIG. 6 shows an example of using this to obtain an odor distribution image. FIG. 6A shows a schematic diagram of an arrangement for obtaining an odor distribution image, and FIG. 6B shows an example of the obtained odor distribution image. In FIG. 6 (b), from a to d, the odor image was acquired immediately after the smell: a: 10 seconds, c: 30 seconds, d: 50 seconds. Looking at the images from A to D, it can be seen that the temporal change of the odor image is obtained.

  In the above case, the adsorbing sheet is a mixture of 20% fluorescent dye aqueous solution and 80% glycerin solution. Glycerin is used to prevent the adsorbing sheet from drying and adhere to the acrylic plate. Glycerin and an acrylic plate are desirable materials because they are transparent to 254 nm excitation light and can ignore fluorescence. This mixed solution can be used by impregnating paper or cloth that can ignore fluorescence with application or impregnation.

  In addition, various fluorescent probes (fluorescent dyes) that interact differently with odorous substances can be used as the fluorescent material dispersed in the adsorption sheet. These can also be used simultaneously by making it into the shape of one adsorption sheet, stripe shape, or mosaic shape. For example, acridine orange, fluorescein, pyrene, allyl naphthalene sulfonic acid, tryptophan, quinine sulfate, fluorescent peptide, quantum dot ZiSe, etc. . FIG. 2 shows the odor substance, furaldehyde (Acridine Orange), fluorescein, fluorescein, pyrene, quinine sulfate, tryptophan, and the like when used as fluorescent dyes. It shows the extinction rate for Furaldehyde, Vanillin, Benzene, and NPOE (Nitrophenyl Octyl Ether). It can be seen that pyrene has almost uniform sensitivity to these odorous substances. FIG. 3 shows the wavelength dependence of the extinction rate when furaldehyde is adsorbed on quinine sulfate (Quinine Sulfate). From this figure, it can be seen that when the comparison is made using the fluorescence intensity difference, the difference at the wavelength position of the fluorescence peak may be used.

  As described above, the use of a fluorescent dye that is quenched by adsorbing an odorous substance has an advantage that the imaging device 3 can be prevented from being saturated by excessive input.

There are the following methods for forming the fluorescent dye into a film.
1) Mix in glycerin or water-retaining polymer (gel) as an adsorbing material and make it into a thin sheet.
2) It is mixed, adsorbed or soaked into a group of polymer beads of about 10 nm to 100 μm and leveled into a sheet.
By making each polymer bead group using multiple fluorescent dyes and mixing these polymer bead groups, it easily consists of multiple areas, and when each area is irradiated with the same excitation light Those containing respective fluorescent dyes that emit fluorescence of different wavelengths can be prepared.

  In this case, the odor information can be extracted by selecting the mixed fluorescent dye by the combination of the excitation wavelength and the fluorescent wavelength of the fluorescent dye, or the combination of the fluorescent wavelength. For example, in combination of fluorescence wavelengths, quinine is 330 nm and 380 nm, tryptophan is 280 nm and 360 nm, and ANS of allylnaphthalene sulfonic acids is 350 nm and 515 nm. For excitation, light from a mercury lamp or the like is irradiated through a high-pass filter, and the fluorescence image is filtered by a low-pass filter or a band-pass filter and then captured by an imaging device such as the imaging device.

  By using a plurality of the above adsorbing sheets, it is possible to measure the distribution of a wide range of odorous substances. In this case, after the odor substance is adsorbed on the adsorbing sheet, an adsorption inhibiting layer that inhibits further adsorption is formed. As the adsorption-inhibiting layer, a thin film may be attached, or for example, an acrylic adhesive may be applied and fixed by spraying or the like.

DESCRIPTION OF SYMBOLS 1 Adsorption sheet 2 Filter 3 Imaging device 4 Excitation light source 5 Dark box 6 Display device

Claims (10)

An odor imaging device for imaging an odor substance distribution,
An adsorption sheet having an adsorption surface for adsorbing odorous substances;
An excitation light source for irradiating the adsorption sheet with excitation light;
An imaging device for imaging the fluorescence intensity distribution on the adsorption sheet by the excitation light;
A display device that displays, as image data, the amount of change in the fluorescence intensity distribution from the imaging device,
The odor distribution imaging apparatus according to claim 1, wherein the adsorbing sheet is provided with an adsorbing material including a fluorescent dye that changes fluorescence of a predetermined wavelength by adsorbing a predetermined odor substance.   2. The odor distribution imaging apparatus according to claim 1, wherein the adsorption sheet reduces the fluorescence emission intensity by adsorbing the odor substance.   The adsorbing sheet is obtained by applying or impregnating the adsorbing material to a cloth or paper-like porous material that is stretched on the surface of a flat plate that transmits the excitation light and does not emit fluorescence in the fluorescence wavelength band. The odor distribution imaging apparatus according to any one of claims 1 and 2.   The said adsorption sheet consists of several area | regions, and when each area | region receives irradiation of the same excitation light, it contains each fluorescent dye which emits the fluorescence of a different wavelength, The Claims 1-3 characterized by the above-mentioned. The odor distribution imaging apparatus according to any one of the above.   5. The fluorescent dye is any one of acridine orange, fluorescein, pyrene, allyl naphthalene sulfonic acid, tryptophan, quinine sulfate, fluorescent peptide, and quantum dot ZiSe. The odor distribution imaging apparatus according to any one of the above.   6. The odor distribution imaging according to claim 1, further comprising forming an adsorption inhibition layer that inhibits further progress of adsorption after adsorbing an odor substance on the adsorption sheet. apparatus.   The adsorbing sheet is detachable from the odor distribution imaging device. When the odor substance is adsorbed to the adsorbing sheet, the adsorption sheet is separated from the odor distribution imaging device and irradiated with the excitation light. The odor distribution imaging apparatus according to any one of claims 1 to 6, wherein the odor distribution imaging apparatus is attached to the odor distribution imaging apparatus.   8. The adsorbent sheet according to claim 1, wherein a mixture of a fluorescent dye solution and glycerin or a water-soluble polymer is applied or impregnated on a cloth or a paper-like sheet on an acrylic plate. The odor distribution imaging apparatus according to any one of the above.   The time change of the intensity distribution of the fluorescence is displayed on the display device by using a sheet in which a quinine sulfate solution using water and a glycerin aqueous solution as a solvent is adsorbed on an acrylic plate. The odor distribution imaging apparatus according to any one of claims 1 to 5.   10. The adsorbent sheet according to claim 1, wherein a fluorescent dye is mixed, adsorbed or soaked in a group of polymer beads having a diameter of 10 nm to 100 [mu] m, and is averaged into a sheet shape. An odor distribution imaging device according to claim 1.

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