WO2006118077A1 - 光学特性分子導入刺激応答性ゲルおよびこれを用いた外部刺激測定装置並びに外部刺激の測定方法 - Google Patents
光学特性分子導入刺激応答性ゲルおよびこれを用いた外部刺激測定装置並びに外部刺激の測定方法 Download PDFInfo
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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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/645—Specially adapted constructive features of fluorimeters
- G01N21/6452—Individual samples arranged in a regular 2D-array, e.g. multiwell plates
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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
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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
- G01N21/7703—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 using reagent-clad optical fibres or optical waveguides
- G01N2021/7706—Reagent provision
- G01N2021/7723—Swelling part, also for adsorption sensor, i.e. without chemical reaction
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T436/00—Chemistry: analytical and immunological testing
- Y10T436/13—Tracers or tags
Definitions
- the present invention relates to an optical property molecule-introduced stimulus-responsive gel, an external stimulus measurement apparatus using the same, and a method for measuring an external stimulus. Particularly, volume change according to an external stimulus is easily and reliably performed.
- the present invention relates to an optical property molecule-introduced stimulus-responsive gel that can be converted into optical information, an external stimulus measuring device using the gel, and an external stimulus measuring method.
- a stimulus-responsive gel that undergoes a volume change due to swelling or contraction in response to an external stimulus such as pH, temperature, or ion concentration has a high possibility as a sensor element or the like.
- the volume change has mainly been evaluated by volume measurement with a microscope or weight measurement with a balance.
- this method when a new system is constructed by actually using the stimulus-responsive gel as a sensor element, it becomes a big obstacle in handling.
- Patent Document 1 JP 2001-505236 (published on April 17, 2001)
- Patent Document 2 JP 2004-27195 (published on January 29, 2004)
- Patent Document 3 Japanese Patent Laid-Open No. 2000-266676 (published September 29, 2000)
- Patent Document 4 Japanese Patent Laid-Open No. 11-228850 (published August 24, 1999)
- Patent Document 5 JP 2001-33832 (published on February 9, 2001)
- Patent Document 6 JP 2005-10490 (published on January 13, 2005)
- Non-Patent Document 1 JH Holtz, SA Asher, Nature, 389, 829-832 (1997)
- the present invention has been made in view of the above-described problems, and its object is to provide a stimulus-responsive gel that can easily and reliably convert a volume change in response to an external stimulus into optical information. Another object of the present invention is to provide an external stimulus measuring device and an external stimulus measuring method using the same.
- the optical property molecule-introduced stimulus-responsive gel has an optical property molecule introduced into the stimulus-responsive gel that changes in volume in response to an external stimulus.
- An optical property molecule-introduced stimulus-responsive gel wherein the optical property molecule is a molecule having a fluorescent chromophore, or a molecule that absorbs visible light or ultraviolet light.
- the content of the molecule having the fluorescent chromophore or the molecule that absorbs visible light or ultraviolet light depends on the concentration of the molecule having the fluorescent chromophore in the stimulus-responsive gel, or the optical property molecule introduction stimulus response.
- Range in which the concentration of molecules that absorb visible light or ultraviolet light in the crystalline gel is approximately proportional to the fluorescence intensity of the above-mentioned optical property molecule introduction stimuli-responsive gel or the absorbance of visible light or ultraviolet light It is characterized by being.
- the content of the molecule having a fluorescent chromophore or a molecule that absorbs visible light or ultraviolet light is an optical property molecule in a dry state. It is preferably 0.001% by weight or more and 30% by weight or less when the introduced stimulus-responsive gel is 100% by weight.
- the molecule having the fluorescent chromophore or the molecule absorbing visible light or ultraviolet light is introduced into the optical property molecule by chemical bonding. It is preferably introduced into a stimulus-responsive gel. Further, the molecule having the fluorescent chromophore or the molecule that absorbs visible light or ultraviolet light may be introduced into the optical property molecule-introduced stimulus-responsive gel by electrostatic interaction or hydrogen bonding.
- the optical characteristic molecule introduction stimulus-responsive gel is stimulated.
- the liquid that is absorbed or released is preferably water or an organic solvent.
- the liquid that is absorbed or released may be an organic solvent.
- the external stimulus is pH, ion concentration, heat, electricity, a molecule to be recognized, a signal indicating a change in a biological state, a magnetic field, or light. It is preferable.
- An external stimulus measurement device includes an optical characteristic molecule-introduced stimulus-responsive gel according to the present invention and a liquid that is absorbed or released by the optical property molecule-introduced stimulus-responsive gel in response to an external stimulus. Exposing the optically characteristic molecule-introduced stimulus-responsive gel to an external stimulus to cause a volume change and irradiating the sample part with light of a specific wavelength to obtain fluorescence intensity or absorbance of visible light or ultraviolet light. It includes at least an optical information measuring unit for measuring.
- the external stimulus measurement device further includes an optical information output unit that converts the fluorescence intensity measured by the optical information measurement unit or the absorbance of visible light or ultraviolet light into an electrical signal and outputs the electrical signal. It is preferable to include.
- the external stimulus measurement device further includes an external stimulus that causes a volume change of the optical property molecule introduction stimulus-responsive gel from the electrical signal output from the optical information output unit. It is preferable to include an arithmetic processing unit that calculates the size.
- the arithmetic unit stores a calibration curve indicating the magnitude of the external stimulus according to the fluorescence intensity or the absorbance of visible light or ultraviolet light.
- the external stimulus is preferably pH, ion concentration, heat, electricity, a molecule to be recognized, a signal indicating a change in a biological state, a magnetic field, or light.
- An external stimulus measurement method that works according to the present invention includes an optical characteristic molecule introduction stimulus-responsive gel that works according to the present invention, and the optical property molecule introduction stimulus-responsive gel absorbs or releases according to the external stimulus.
- the liquid is exposed to known external stimuli of different sizes, causing a volume change in the optical property molecule-introduced stimulus-responsive gel and exposed to external stimuli of the respective sizes.
- a calibration curve indicating the degree of susceptibility, and the optical property molecule-introduced stimulus-responsive gel and the liquid that the optical property molecule-introduced stimulus-responsive gel absorbs or releases in response to external stimuli of unknown size.
- the optical property molecule-introduced stimulus-responsive gel according to the present invention has an optical property in which an optical property molecule is introduced into a stimulus-responsive gel that changes in volume in response to an external stimulus as described above.
- a molecule-introduced stimulus-responsive gel, wherein the optical property molecule is a molecule having a fluorescent chromophore, or a molecule that absorbs visible light or ultraviolet light and the optical property molecule-introduced stimulus-responsive gel described above.
- the content of a molecule having a fluorescent chromophore or a molecule that absorbs visible light or ultraviolet light is determined by the concentration of the molecule having the fluorescent chromophore in the stimulus-responsive gel or the introduction of the optical characteristic molecule.
- the concentration of molecules that absorb visible light or ultraviolet light in the stimulus-responsive gel is approximately proportional to the fluorescence intensity of the above-mentioned optical property molecule-introduced stimulus-responsive gel or the absorbance of visible light or ultraviolet light.
- the configuration that is Therefore, there is no need for troublesome procedures such as regularly placing particles in the stimulus-responsive gel, and molecules that have a fluorescent chromophore, or visible light or ultraviolet light are used in the production of the optical property molecule-introduced stimulus-responsive gel. It is possible to convert the volume change of the stimulus-responsive gel into optical information by a very simple and reliable method that can be produced simply by introducing light-absorbing molecules.
- the amount of the molecule having a fluorescent chromophore to be introduced or a molecule that absorbs visible light or ultraviolet light is small, the properties of the stimulus-responsive gel itself are hardly impaired.
- FIG. 1 is a view showing a chemical reaction formula for synthesizing a butyl group-introduced 5- (2,1-aminoethyl) aminonaphthalene 1-sulfonic acid (EDANS) in Examples.
- FIG. 2 is a view showing a chemical reaction formula for producing an optical property molecule-introduced stimulus-responsive gel (PAAc-EDANS gel) into which a fluorescent chromophore is introduced in Examples.
- PAAc-EDANS gel optical property molecule-introduced stimulus-responsive gel
- FIG. 3 is a graph showing the swelling ratio (volume change) of cylindrical PA Ac-EDANS gel in various concentrations of NaCl aqueous solution in Examples.
- FIG. 4 is a graph showing the swelling ratio (weight change) of plate-like PAAc EDANS gel in various concentrations of NaCl aqueous solution in Examples.
- FIG. 5 is a graph showing the relationship between the swelling rate (volume change) and fluorescence intensity of cylindrical PAAc-EDANS gel in Examples.
- FIG. 6 is a graph showing the relationship between relative fluorescence intensity and swelling rate (volume change) of cylindrical PAAc-EDANS gel in Examples.
- FIG. 7 is a graph showing the relationship between the swelling ratio (weight change) of plate-like PAAc-EDANS gel and relative fluorescence intensity in Examples.
- FIG. 8 is a diagram schematically showing the relationship between the swelling ratio and fluorescence intensity of the optical property molecule-introduced stimulus-responsive gel of the present invention.
- FIG. 9 is a diagram showing a configuration in which a plurality of gel chips using the optically characteristic molecule-introduced stimulus-responsive gel of the present invention are arranged in an array.
- FIG. 10 is a schematic diagram showing an example of an atherogenic 6-amino compound used in the Examples to produce an optically characteristic molecule-introduced stimulus-responsive gel (EDANS-introduced BPA-responsive gel) that responds to bisphenol A.
- FIG. 3 is a diagram showing a method for synthesizing 1-deoxy- ⁇ -cyclodextrin.
- FIG. 11 is a diagram showing a method for producing an optical property molecule-introduced stimulus-responsive gel (EDANS-introduced BPA-responsive gel) that responds to bisphenol wrinkles in Examples.
- EDANS-introduced BPA-responsive gel optical property molecule-introduced stimulus-responsive gel
- FIG. 12 shows a cylindrical EDANS guide in an aqueous bisphenol A solution in the example.
- 5 is a graph showing the change over time in the swelling rate (volume change) when an input BPA-responsive gel is immersed.
- FIG. 13 is a diagram showing the results of fluorescence microscope observation of EDANS-introduced BPA-responsive gels carried out at 0 hours, 6 hours and 24 hours after immersion in a bisphenol A aqueous solution in Examples.
- FIG. 14 is a graph showing the fluorescence intensity of an EDANS-introduced BPA-responsive gel immersed in a bisphenol aqueous solution calculated by image analysis of a fluorescence micrograph.
- FIG. 15 is a graph showing the relationship between the fluorescence intensity and the swelling ratio (volume change) of the EDANS-introduced BPA-responsive gel.
- the present inventors have determined the concentration and fluorescence intensity of molecules having a fluorescent chromophore in order to convert the volume change of the stimulus-responsive gel into optical information simply and reliably.
- molecules having a fluorescent chromophore or molecules having a fluorescent chromophore and visible light or ultraviolet light are in a concentration range in which the concentration of the molecule that absorbs visible light or ultraviolet light has a proportional relationship with the fluorescence intensity or absorbance, respectively.
- volume changes could be converted into optical information as changes in fluorescence intensity and absorbance.
- an optical characteristic molecule-introduced stimulus-responsive gel into which a fluorescent chromophore was introduced was produced, and the volume change at various ion concentrations was actually measured, and the fluorescence intensity was measured. I investigated the relationship. As a result, it was found that there is a clear linear relationship in the logarithmic plot of volume change and fluorescence intensity.
- the present inventors have found that the optical property molecule-introduced stimulus-responsive gel into which a molecule having a fluorescent chromophore or a molecule that absorbs visible light or ultraviolet light is introduced exhibits a change in volume due to an external stimulus as fluorescence intensity or Absorbance and It was found that the external stimulus can be measured by measuring fluorescence intensity or absorbance by using the gel with stimulating molecule responsive to introduction of optical characteristics molecule of the present invention. It came to complete.
- (I) the optical property molecule-introduced stimulus-responsive gel according to the present invention, (II) an external stimulus measuring device, and (III) a method for measuring an external stimulus will be described in this order.
- the optical property molecule-introduced stimulus-responsive gel of the present invention has a configuration in which an optical property molecule is introduced into a stimulus-responsive gel that changes in volume in response to an external stimulus.
- the optical property molecule means a molecule having a fluorescent chromophore or a molecule that absorbs visible light or ultraviolet light.
- the optical property molecule-introduced stimulus-responsive gel according to the present invention is a stimulus-responsive gel, and shows a signal, a magnetic field, or a signal indicating changes in pH, ion concentration, heat, electricity, recognized molecule, biological state, and the like. It is a gel that absorbs or releases a liquid by an external stimulus such as light and swells or contracts to cause a volume change.
- the volume change according to the external stimulus of the optically characteristic molecule-introduced stimulus-responsive gel of the present invention may be reversible or irreversible, but is reversible. Is more preferable. The reversibility is preferable because the gel can be used repeatedly and can be used as a reproducible sensor material.
- the amount of volume change when the optical property molecule-introduced stimulus-responsive gel according to the present invention undergoes a volume change in response to an external stimulus is not particularly limited, but the higher the volume change amount, the better.
- the volume specific force during swelling and shrinkage is more preferably 2 or more, more preferably 5 or more, and even more preferably 10 or more.
- the volume change amount is 2 or more, it is possible to change the concentration of molecules having fluorescent chromophores or molecules that absorb visible light or ultraviolet light due to volume changes of the gel with stimulating response to the introduction of optical characteristic molecules. Detect and convert volume changes into optical information.
- volume change the greater the change in the concentration of molecules with fluorescent chromophores or molecules that absorb visible light or ultraviolet light due to volume changes in the optical property molecule-introduced stimulus-responsive gel. This is preferable because the sensitivity is improved.
- the optical property molecule introduction stimulus-responsive gel introduces an optical property molecule, that is, a molecule having a fluorescent chromophore, or a molecule that absorbs visible light or ultraviolet light. It is what has been. This makes it possible to convert volume changes in response to external stimuli of the molecule-introduced stimulus-responsive gel into optical information by measuring fluorescence intensity or absorbance of visible light or ultraviolet light. Become.
- the content of the molecule having a fluorescent chromophore or a molecule that absorbs visible light or ultraviolet light in the optical property molecule-introduced stimulus-responsive gel of the present invention is determined according to the optical property molecule-introduced stimulus-responsive gel.
- the concentration of a molecule having a fluorescent chromophore in the molecule, or the concentration of a molecule that absorbs visible light or ultraviolet light in the stimulus-responsive gel is determined by the fluorescence intensity of the optical property molecule-introduced stimulus-responsive gel or visible light or It is preferably in a range that is approximately proportional to the absorbance of ultraviolet light.
- the fluorescence intensity of the optical property molecule-introduced stimulus-responsive gel in which the volume change occurs in response to an external stimulus, or the absorbance of visible light or ultraviolet light, and the molecule having the fluorescent chromophore in the stimulus-responsive gel Alternatively, the concentration of molecules that absorb visible light or ultraviolet light is proportional.
- the concentration of the color material is equal to or higher than the saturated absorption concentration.
- the saturation absorption concentration or higher is because the relationship between the color material concentration and the light absorption amount is a linear relationship. The power disclosed that the colorant density is so high as to deviate greatly. In the present invention, such a linear relationship is used.
- the content of the molecule having a fluorescent chromophore or a molecule that absorbs visible light or ultraviolet light in the optical property-molecule-introduced stimulus-responsive gel of the present invention is within a range in which the above-described relationship is satisfied. As long as it is 100% by weight, it is preferable that the content is not less than 0.00001% by weight and not more than 80% when the dried optical property molecule-introduced stimulus-responsive gel is 100% by weight. 0. 001 wt% or more 50% or less is more preferable 0. 001 wt% or more 30% or less is more preferable 0.01 wt% or more 10 wt% The following is particularly preferred: 0.1% by weight or more and 5% by weight or less is most preferred.
- the volume change can be suitably converted into optical information.
- the content of the molecule having a fluorescent chromophore or a molecule that absorbs visible light or ultraviolet light is smaller than 80% by weight, the fluorescence intensity or absorbance, and the molecule having a fluorescent chromophore or the like can be reduced. From the proportional relationship of the concentration, the volume change can be suitably converted into optical information.
- the smaller the content of the molecule having the fluorescent chromophore or the molecule that absorbs visible light or ultraviolet light the smaller the molecule having the fluorescent chromophore.
- the content of the molecule having a fluorescent chromophore or a molecule that absorbs visible light or ultraviolet light in the optical characteristic molecule introduction stimulus-responsive gel of the present invention is determined as follows. When the stimuli-responsive gel is 100% by weight, it is more preferably 30% by weight or less.
- the optical property molecule-introduced stimulus-responsive gel of the present invention is one in which a molecule having a fluorescent chromophore or a molecule that absorbs visible light or ultraviolet light is introduced.
- introduction refers to a molecule having a fluorescent chromophore when an optical property molecule-introduced stimulus-responsive gel absorbs or releases a liquid in response to an external stimulus to cause a volume change. As long as molecules that absorb visible light or ultraviolet light are not released together with the liquid, the optical properties may be retained in the molecule-introduced stimulus-responsive gel.
- a molecule having a fluorescent chromophore or a molecule that absorbs visible light or ultraviolet light is combined with the liquid.
- a molecule having a fluorescent chromophore or visible light molecules that absorb ultraviolet light are held in the optical property molecule-introduced stimulus-responsive gel by chemical bonds such as ionic bonds and covalent bonds. Preferably it is.
- a hydrogen bond or electrostatic interaction is performed so that a molecule having a fluorescent chromophore or a molecule that absorbs visible light or ultraviolet light is not released to the outside in the cross-linked structure of the optical property molecule introduction stimulus-responsive gel. Or may be physically held in a crosslinked network structure.
- the molecule having a fluorescent chromophore is not particularly limited, and any molecule having a fluorescent chromophore may be used.
- Specific examples of the molecule having such a fluorescent chromophore include, for example, anthracene, rhodamine, funorescein, Yin-sin, coumarin, erythrucine, atalidine, pyrene, stilbene, naphthalene, nitrobenzoxazazole, quinoline, Examples include acid aldehyde, carbazole, pyridinium, and derivatives thereof.
- a molecule that absorbs visible light is not particularly limited, and various dyes and pigments can be used. Specific examples of the molecules that absorb visible light include azo dyes such as methyl yellow, methyl orange, and methyl red, and cyanine dyes such as anthocyanin and phthalocyanine.
- the molecule that absorbs ultraviolet light is not particularly limited, and specific examples include anthracene, melanin dye, flavone, benzophenone, nucleic acid, protein, and the like.
- the polymer constituting the molecule-introduced stimulus-responsive gel of the present invention includes a signal indicating a change in pH, ion concentration, recognized molecule, electricity, heat, biological state, magnetic field, light, etc.
- a stimulus-responsive gel that swells or contracts due to external stimuli, and specifically changes its volume depending on pH and ion concentration.
- Gels include, for example, poly (meth) acrylic acid, polymaleic acid, polybutyl sulfonic acid, polybulubenzene sulfonic acid, polyacrylamide alkyl sulfonic acid, polyacrylamide alkyl sulfonic acid, polydimethylaminopropyl (meth) acrylamide.
- stimuli-responsive gels that change in volume according to pH and ion concentration include poly (meth) acrylic acid, (meth) acrylic acid and (meth) acrylamide, and hydroxyethyl (meth) acrylate.
- acrylic or “methacrylic” is represented as “ ⁇ (meth) acrylic” when it also means a deviation.
- the stimulus-responsive gel that causes a volume change according to the molecule to be recognized is not particularly limited.
- an enzyme, an antigen, an antibody, a nucleic acid, or the like as a substance to be recognized can be used. Examples include those fixed to a stimulus-responsive gel that changes in volume according to the pH, ion concentration, heat, etc. described above. Further, it may be imprinted with the shape of the molecule recognized by the stimulus-responsive gel that changes in volume according to the pH, ion concentration, heat, etc. described above.
- a stimulus-responsive gel absorbs or releases a liquid in response to an external stimulus and swells or contracts to cause a volume change.
- the liquid that is absorbed or released during swelling or shrinkage is not particularly limited, and may be water or an aqueous buffer solution, or an organic solution. It may be a solvent. Specific examples of such liquids include water; aqueous buffers such as phosphate buffers; methanol, ethanol, 1 propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, and isopentyl.
- Alcohols such as alcohol; acetone, 2-butanone, Ketones such as 3-pentanone, methyl isopropyl ketone, methyl n-propyl ketone, 3-hexanone and methyl n-butyl ketone; ethers such as jetyl ether, diisopropyl ether, tetrahydrofuran, tetrahydropyran; esters such as acetate ethyl ester; Amides such as methylformamide and dimethylacetamide; dimethyl sulfoxide; nitriles such as acetonitrile; propylene carbonate; lower saturated hydrocarbons such as pentane, hexane and cyclohexane; xylene; toluene; or two or more of these It is possible to mention a mixture of these.
- the shape of the optically characteristic molecule-introduced stimulus-responsive gel according to the present invention is not particularly limited, and may be any shape, and a preferred shape may be appropriately selected according to the intended use.
- Examples of the shape that can be applied include a cylindrical shape, a plate shape, a film shape, a particle shape, and a rectangular parallelepiped shape.
- a plate shape, a film shape or the like is preferable.
- a method of injecting a monomer composition or the like, which is a raw material of the optical property molecule introduction stimulus-responsive gel, into a desired mold before polymerization, and performing polymerization can be used. it can.
- the size of the optical property molecule-introduced stimulus-responsive gel is not particularly limited, and V may be any size. U is preferred depending on the application, and the size may be appropriately selected. .
- the optical property molecule-introduced stimulus-responsive gel is a molecule having a fluorescent chromophore or a molecule that absorbs visible light or ultraviolet light absorbs or releases a liquid in response to an external stimulus.
- these molecules are, for example, in the optical property molecule-introduced stimulus-responsive gel so that they are not released together with the liquid when the volume change occurs and are retained in the optical property-molecule-introduced stimulus-responsive gel. , Manufactured to be chemically bonded.
- a molecule having a fluorescent chromophore introduced with a polymerizable group or a visible light or ultraviolet light introduced with a polymerizable group is absorbed during polymerization of an optical property molecule-introduced stimulus-responsive gel.
- a method in which the molecule to be polymerized is added to a monomer that forms the main chain of an optical property molecule introduction stimulus-responsive gel.
- Stimulus-responsive gels with introduction of optical molecules are molecules that have a fluorescent chromophore introduced with a polymerizable group, or molecules that absorb visible or ultraviolet light that have introduced a polymerizable group, monomers that form a main chain, and initiation. It can be easily produced by dissolving an agent, a crosslinking agent or the like in an appropriate solvent, or by polymerizing with an external force of heat, light or the like without using a solvent.
- an enzyme, antigen, antibody, nucleic acid, or the like as a substance to be recognized is further introduced with a polymerizable group. Add it to polymerize.
- polymerization is carried out by adding a molecule that recognizes that the molecule to be recognized is introduced with a polymerizable group to the ligand that specifically binds to the molecule to be recognized. After that, the polymer force that gives the molecules to be recognized afterwards can be removed as well.
- both may be added, or a molecule that recognizes a ligand introduced with a polymerizable group may be added. It may be added after inclusion.
- the group to be introduced is not particularly limited as long as it is a group capable of chemically binding to the polymer compound forming the network structure of the polymer gel.
- a vinyl group, (Meth) atallyloyl group, hydroxyl group, carboxyl group, amino group and the like can be mentioned.
- the monomer may be any monomer that constitutes the main chain of the polymer that constitutes the optical property molecule introduction stimulus-responsive gel as described above.
- (meth) acrylic may be used. Acid, maleic acid, vinyl sulfonic acid, butyl benzene sulfonic acid, acrylamide alkyl sulfonic acid, acrylamide alkyl sulfonic acid, dimethylaminopropyl (meth) acrylamide, (meth) acrylonitrile, bulu sulfonic acid, bulubenzene sulfonic acid, dimethyl Amino-substituted (meth) acrylamides such as minopropyl (meth) acrylamide, (meth) acrylamide, dimethylaminoethyl (meth) acrylate, jetylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, etc.
- esters steel Emissions, vinyl pyridine, vinyl carbazole, dimethylamino styrene, N- isopropyl Alkyl-substituted (meth) acrylamides such as (meth) acrylamide can be used alone or in combination of two or more.
- the cross-linking agent is not particularly limited, and specifically, for example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, N, N, —Methylene bisacrylamide, tolylene diisocyanate, dibutylbenzene, polyethylene glycol di (meth) acrylate, and the like.
- the polymerization initiator is not particularly limited, and examples thereof include persulfates such as ammonium persulfate, sodium persulfate, and ammonium persulfate; hydrogen peroxide; t- Peroxides such as butyl hydride-peroxide and cumene hydride-peroxide, azobis thiol-tolyl, peroxybenzoyl and the like can be preferably used.
- persulfates such as ammonium persulfate, sodium persulfate, and ammonium persulfate
- hydrogen peroxide hydrogen peroxide
- t- Peroxides such as butyl hydride-peroxide and cumene hydride-peroxide, azobis thiol-tolyl, peroxybenzoyl and the like
- initiators exhibiting acidity such as persulfates and baroxides include, for example, sodium bisulfite, N, N, ⁇ ′, ⁇ , and
- the production method in which a molecule having a fluorescent chromophore or a molecule that absorbs visible light or ultraviolet light is introduced into the optical property molecule introduction stimulus-responsive gel by chemical bonding is described above.
- a molecule having a fluorescent chromophore or a molecule that absorbs visible light or ultraviolet light is introduced so as to be chemically bonded.
- Examples of such a method include a polymer having a reactive functional group such as a hydroxyl group or a force lpoxyl group (polyvinyl alcohol, cellulose, polyacrylic acid, etc.) or a crosslinked product thereof, and a fluorescent chromophore having a reactive functional group.
- a target optical property molecule by bonding a molecule, a visible light absorbing molecule having a reactive functional group, or an ultraviolet light absorbing molecule having a reactive functional group by a reaction (polymer reaction) between the functional groups.
- a method for producing a stimulus-responsive gel can be mentioned.
- a molecule having a fluorescent chromophore or a molecule that absorbs visible light or ultraviolet light is physically formed into a crosslinked network structure so that the molecule is not released to the outside of the optical property molecule-introduced stimulus-responsive gel. You may manufacture by hold
- a fluorescent chromophore is provided after polymerization of a monomer composition of an optical property molecule introduction stimulus-responsive gel.
- the optical property molecule-introduced stimulus-responsive gel according to the present invention is introduced with a molecule having a fluorescent chromophore or a molecule that absorbs visible light or ultraviolet light.
- the volume change of the introduced stimulus-responsive gel can be converted into optical information as a change in fluorescence intensity or a change in absorbance, and can be used as a simple system when the optical property molecule-introduced stimulus-responsive gel is used as a sensor element. Therefore, it is not necessary to use a method to measure volume changes according to external stimuli such as volume measurement with a microscope or weight measurement with a balance, etc., and optical measurement results such as fluorescence intensity and absorbance can be obtained. It can be used as it is as a quantitative indication of volume change.
- the optical property molecule-introduced stimulus-responsive gel of the present invention by using the optical property molecule-introduced stimulus-responsive gel of the present invention, the volume change of the optical property molecule-introduced stimulus-responsive gel in response to an external stimulus is converted into optical information.
- An external stimulus measurement device that detects or measures a stimulus is also included in the present invention.
- ⁇ is the extinction coefficient of the fluorescent molecule
- 1 is the length of the sample to be measured.
- equation (2) if the relationship between the concentration of the fluorescent chromophore in the gel and the fluorescence intensity is applied to a reference solution without external stimulation and to a stimulation solution that gives external stimulation such as ion concentration, equation (2) is obtained. It is done.
- the absolute amount n of the fluorescent chromophore present in the gel is constant, and therefore has the following relationship.
- An external stimulus measuring device includes an optical characteristic molecule introduction stimulation-responsive gel of the present invention and a liquid that the optical characteristic molecule introduction stimulation-responsive gel absorbs or releases in response to external stimulation.
- An optical sample that measures the fluorescence intensity or the absorbance of visible light or ultraviolet light by irradiating light of a specific wavelength to the sample part where the characteristic molecule-introduced stimulus-responsive gel is exposed to external stimuli and undergoes a volume change. And at least an information measuring unit.
- the sample portion includes at least the optical property molecule-introduced stimulus-responsive gel of the present invention and a liquid that is absorbed or released by the optical property molecule-introduced stimulus-responsive gel in response to an external stimulus.
- the liquid comes into contact with the optical property molecule-introduced stimulus-responsive gel so as to be freely absorbed and released by the optical property-molecule-introduced stimulus-responsive gel!
- Introducing molecules with optical properties Stimulus-responsive gel is exposed to external stimuli such as pH, ion concentration, heat, electricity, molecules to be recognized, signals indicating changes in biological state, magnetic fields, or light in the sample part.
- the coexisting liquid is absorbed or released to cause a volume change.
- the sample part can bring the solution or molecule as the external stimulus into contact with the optical property molecule-introduced stimulus-responsive gel. It is necessary to be connected. Further, when heat, electricity, etc. are external stimuli, it is not always necessary to contact them with the optical characteristic molecule-introduced stimulus-responsive gel, so the sample part may be a closed system. Further, the size and number of samples in the sample part may be appropriately selected according to the purpose. For example, when many measurements are made simultaneously As shown in FIG. 9, a configuration in which a plurality of gel chips are arranged in an array may be employed.
- the optical information measuring unit may measure the fluorescence intensity or the absorbance of visible light or ultraviolet light by irradiating the sample part with light of a specific wavelength! / .
- the stimulus molecule responsive to introduction of an optical characteristic molecule used in the external stimulus measurement device of the present invention is one in which a molecule having a fluorescent chromophore is introduced, the sample portion is irradiated with excitation light. Then, the intensity of the generated fluorescence is measured.
- the method for measuring the fluorescence intensity is not particularly limited, and may be appropriately selected according to the shape of the optical property molecule-introduced stimulus-responsive gel.
- a method for measuring fluorescence intensity for example, a method of measuring fluorescence intensity using a fluorescence spectrophotometer, a method of performing fluorescence microscope observation and obtaining fluorescence intensity by image analysis, and the like can be used.
- the method for obtaining the fluorescence intensity by image analysis is not particularly limited.
- the fluorescence microscope image is read into a computer, converted into a grayscale image using image analysis software, and the brightness of the image is obtained. After the histogram is displayed, a method for calculating the relative strength of the value force can be mentioned.
- image analysis software any image analysis software can be used as long as the image analysis software can form a histogram of images without limitation.
- the optical property molecule introduction stimulus-responsive gel used in the external stimulus measurement apparatus of the present invention has introduced a molecule that absorbs visible light or ultraviolet light
- Irradiation with light of a specific wavelength that is absorbed by the introduced molecule may be performed to measure absorption of reflected light or transmitted light, and measure absorbance.
- the optical property molecule-introduced stimulus-responsive gel used in the external stimulus measurement device of the present invention is a molecule into which a molecule that absorbs visible light is introduced, the amount of absorption is visually determined. It is also possible to confirm.
- the external stimulus measurement apparatus further includes an optical information output unit that converts the fluorescence intensity measured by the optical information measurement unit or the absorbance of visible light or ultraviolet light into an electrical signal and outputs the electrical signal. It is more preferable that it contains. As a result, it is possible to obtain the change in volume of the optically responsive molecule-introduced stimulus-responsive gel in response to an external stimulus as an electrical signal that can be handled as data and can be readily automated.
- the external stimulus measurement device further causes a volume change of the optical property molecule introduction stimulus-responsive gel from the electrical signal output from the optical information output unit.
- an arithmetic processing unit for calculating the magnitude of the external stimulus.
- the calculation unit stores a calibration curve indicating the magnitude of the external stimulus according to the fluorescence intensity or the absorbance of visible light or ultraviolet light. The calibration curve is obtained by applying external stimuli of various sizes in advance, and obtaining the volume change of the optical property molecule-introduced stimulus-responsive gel corresponding to the external stimulus as optical information such as fluorescence intensity and absorbance. It is determined to show the correlation.
- the external stimulus measurement device of the present invention is not limited to the purpose of detecting and measuring the size of the external stimulus, but stores optical information values corresponding to a certain amount of external stimulus, and the external stimulus is more than that. It is also very effective when making the following judgments.
- the optical property molecule-introduced stimulus-responsive gel according to the present invention has a molecule having a fluorescent chromophore or a molecule that absorbs visible light or ultraviolet light is introduced, so that an optical property molecule-introduced stimulus by an external stimulus is introduced.
- the volume change of the responsive gel can be converted into optical information as a change in fluorescence intensity or a change in absorbance, and can be used as a simple system when using the optically characteristic molecule-introduced stimulus-responsive gel as a sensor element.
- the volume change of the optical property molecule-introduced stimulus-responsive gel in response to the external stimulus is converted into optical information, and the optical information is converted into the external stimulus.
- a method for measuring an external stimulus that detects or measures the above is included in the present invention.
- the external stimulus measurement method includes the optical characteristic molecule introduction stimulation-responsive gel of the present invention and a liquid that is absorbed or released by the optical characteristic molecule introduction stimulation-responsive gel in response to external stimulation.
- a liquid that is absorbed or released by the optical characteristic molecule introduction stimulation-responsive gel in response to external stimulation Exposed to known external stimuli of different sizes to cause changes in volume of optically responsive molecule-introduced stimuli-responsive gels, identified as optically responsive molecule-introduced stimuli-responsive gels exposed to different sized external stimuli Irradiating light of a wavelength, measuring fluorescence intensity or absorbance of visible light or ultraviolet light, determining a calibration curve indicating the magnitude of external stimulus according to fluorescence intensity or absorbance of visible light or ultraviolet light; and Optically exposed molecule-stimulated responsive gel and liquid absorbed or released by optically characteristic molecule-introduced stimulus-responsive gel in response to external stimuli are exposed to an external stimulus of unknown size and exposed to light.
- EDANS5 Omg (0.18 mmol)
- sodium hydrogen carbonate 420 mg (5 OO mmol)
- N-succinimidyl acrylate (NSA) 38 mg (0.22 mmol) were stirred with 25 ml of pure water.
- Concentrated hydrochloric acid was added to make it weakly acidic, and acetone was added thereto to precipitate inorganic salts such as sodium hydrogen carbonate, followed by filtration.
- the filtrate was concentrated and fractionated by silica gel chromatography (Wakogel C_200, manufactured by Wako Pure Chemical Industries). The obtained fraction was concentrated, washed with ethyl acetate, vacuum-dried at room temperature, and introduced with a bulene group. -EDANS).
- PAAc-EDANS gel optically characteristic molecule-introduced stimulus-responsive gel
- Purified water 7. 613 g with 2 g acrylic acid (A Ac) and lOOmg / ml bulge EDANSO. 087 ml, 20 mg / ml N, N, 1 ml methylenebisacrylamide (MBAA) O. Add 1 ml of AUM O.
- Example 2 Measurement of volume change of columnar optical characteristic molecule-introduced stimulus-responsive gel
- the cylindrical optical property molecule-introduced stimulus-responsive gel (PAAc—EDA NS gel) produced in Example 1 was sufficiently equilibrated and swollen in pure water, and then each salt-sodium (NaCl) aqueous solution at each concentration was used. And contracted until equilibrium was reached.
- the volume change of the PAAc-EDANS gel was determined as the swelling ratio (volume change) shown in the following formula (11) by measuring the gel diameter change at each concentration of sodium chloride aqueous solution.
- 0 and d are the diameter (cm) of the cylindrical PAAc-EDANS gel in NaCl aqueous solution.
- Fig. 3 shows the swelling ratio (volume change) of cylindrical PAAc-EDANS gel in various concentrations of NaCl aqueous solution.
- the vertical axis represents the swelling ratio (volume change)
- the horizontal axis represents the molar concentration of the NaCl aqueous solution.
- the plate-like optical property molecule-introduced stimulus-responsive gel (PAAc-EDANS gel) produced in Example 1 was sufficiently equilibrated and swollen in pure water, and then dissolved in an aqueous sodium chloride (NaCl) solution at each concentration. And shrunk until equilibrium. The weight change of the PAAc-EDANS gel was measured at each concentration of the sodium chloride aqueous solution to obtain the swelling ratio (weight change) shown in the following formula (12).
- w is the weight of the plate-like PAAc-EDANS gel in water (g), and w is the NaCl aqueous solution.
- Fig. 4 shows the swelling ratio (weight change) of plate-like PAAc-EDANS gel in various concentrations of NaCl aqueous solution.
- the vertical axis indicates the swelling ratio (weight change), and the horizontal axis indicates the molar concentration of the NaCl aqueous solution.
- the swelling ratio decreases with NaCl concentration.
- PAAc-EDANS gel columnar and plate-like optical property molecule-introduced stimulus-responsive gel (PAAc-EDANS gel) produced in Example 1 was sufficiently equilibrated and swollen in pure water, and then placed in a NaCl aqueous solution of each concentration. The PAAc-EDANS gel was shrunk until equilibrium was reached. At each concentration, the columnar PAAc—EDANS gel was attached!
- Epi-illumination fluorescence observation device fluorescence mirror unit U-MWU (excitation filter BP33) attached to an inverted microscope (manufactured by Olympus Corporation: Model IX-70) 0-385, dichroic mirror DM400, absorption filter BA420); Olympus Corporation: IX-FLA type) was observed with a fluorescence microscope.
- FIG. 5 shows the result.
- the fluorescence intensity of the PAAc-EDANS gel in the fluorescence micrograph increases.
- the increase in fluorescence intensity associated with the shrinkage of the PAAc-EDANS gel is caused by the change in the absolute amount of the fluorescent chromophore EDAN S (shown by an ellipse in FIG. 8) in the gel, as schematically shown in FIG.
- the density (concentration) of EDANS increases as a result of the decrease in the volume of the PAAc-EDANS gel.
- the relative fluorescence intensity was calculated, and the relationship between the gel swelling rate (volume change) and the fluorescence intensity was examined.
- the fluorescence intensity was calculated by the following method. First, a fluorescence microscope image was read into a computer and converted into a grayscale image using image analysis software (0 rigin Ver. 7.5). Next, the brightness of the image was displayed as a histogram, and the relative power of the relative intensity was calculated.
- FIG. 6 shows the relationship between the relative fluorescence intensity obtained by image analysis of the fluorescence micrograph of FIG. 5 and the swelling ratio (volume change) of the PAAc-EDANS gel.
- the vertical axis represents the logarithm of relative fluorescence intensity (FZF), and the horizontal axis represents the logarithm of swelling ratio (volume change).
- the relative fluorescence intensity is determined by image analysis to obtain the brightness of the gel.
- the fluorescence intensity (wavelength 480 nm) when excited at a wavelength of 340 nm using a fluorescence spectrophotometer (manufactured by Shimadzu Corporation: RF-5300PC type) was measured.
- Fig. 7 shows the relationship between the swelling ratio (weight variation) of the plate-like PAAc-EDANS gel and the relative fluorescence intensity.
- the fluorescence intensity is a value directly measured by a fluorescence spectrophotometer, and the fluorescence intensity (F) in pure water and in a NaCl aqueous solution are used.
- the horizontal axis represents the logarithm of swelling rate (volume change). From FIG. 7, a clear linear relationship was observed between the logarithmic plots of the swelling ratio (weight change) and the fluorescence intensity, and the slope of the straight line was 0.65 as in the case of the columnar gel. Therefore, in this example, the swelling ratio (weight change) can be treated approximately as the swelling ratio (volume change), and therefore, the ratio between the swelling ratio of the fluorescent chromophore-introduced gel and the fluorescence intensity. A clear correlation was observed regardless of the gel shape, and it was revealed that the fluorescence intensity was proportional to the swelling ratio to the ⁇ 0.65 power.
- B PA bisphenol A
- BPA responsive gel a stimulus responsive gel that responds to bisphenol A
- An optically characteristic molecule-introduced stimulus-responsive gel into which a fluorescent chromophore was introduced was synthesized.
- Optical properties Molecularly-stimulated stimuli-responsive gels were synthesized by synthesizing a stimuli-responsive gel (BPA-responsive gel) by molecular imprinting using cyclodextrin as a ligand that recognizes bisphenol A. This was done by adding a fluorescent chromophore into which the group was introduced. [0081] Synthesis of Ataliloyl 6-amino-6-deoxy- ⁇ -cyclodextrin (acryloyl-CD)>
- Ataliloy 6-amino-6-deoxy- ⁇ -cyclodextrin (acryloyl CD) was synthesized by the method shown in FIG. After reacting ⁇ -cyclodextrin (CD) with anhydrous toluenesulfonic acid (Ts 2 O), the obtained tosyl chloride was converted to sodium azide (NaN
- the aluminide was further reacted with salt alitaroyl in a carbonate buffer solution to synthesize attaloyl-6-amino-6-deoxy- ⁇ -cyclodextrin (acryloyl CD).
- the obtained gel was immersed in 30% acetone aqueous solution to sufficiently remove vertical BPA and allowed to equilibrate and swell in distilled water to obtain the target optical property molecule-introduced stimulus-responsive gel EDANS-introduced BPA-responsive gel.
- EDANS-introduced BPA-responsive gel Prepared.
- Example 7 Measurement of volume change of optical characteristic molecule-introduced stimulus-responsive gel (EDANS-introduced BPA-responsive gel)]
- the swell ratio (volume change) shown in the above formula (11) was determined by measuring the change in the diameter of the gel over time with the immersion time being 0 hours.
- FIG. 12 shows the change over time in the swelling ratio (volume change) when a cylindrical EDANS-introduced BPA-responsive gel is immersed in a bisphenol aqueous solution.
- the vertical axis indicates the swelling rate (volume change), and the horizontal axis indicates time (time).
- the swelling ratio of the EDANS-introduced BPA-responsive gel gradually decreased with the passage of time after immersion. That is, the EDAN S-introduced BPA-responsive gel gradually contracted in the aqueous bisphenol solution.
- Example 8 Observation of fluorescence emission characteristics and measurement of fluorescence intensity of a columnar optical property molecule-introduced stimulus-responsive gel
- the EDANS-introduced BPA-responsive gel was immersed in a bisphenol aqueous solution, and then the EDANS-introduced BPA-responsive gel was observed with a fluorescence microscope. .
- the fluorescence microscope observation was performed in the same manner as in Example 4.
- FIG. 13 shows the results of fluorescence microscope observation of the EDANS-introduced BP A-responsive gel performed at 0, 6, and 24 hours after immersion.
- the fluorescence intensity of the EDANS-introduced BPA-responsive gel in the fluorescence micrograph increases as the EDAN-S-introduced BPA-responsive gel shrinks over time.
- the increase in the fluorescence intensity accompanying the shrinkage of the EDANS-introduced BPA-responsive gel does not change the absolute amount of EDANS, the fluorescent chromophore in the gel, but the volume of the BPA-responsive gel decreases. This is thought to be due to the increase in EDANS concentration. Therefore, by analyzing the image of the fluorescence micrograph at this time, the relative fluorescence intensity was calculated in the same manner as in Example 4, and the relationship between the gel swelling rate (volume change) and the fluorescence intensity was examined.
- Fig. 14 shows bisphenol water solubility calculated by image analysis of fluorescence micrographs.
- the relative fluorescence intensity of the EDANS-introduced BPA-responsive gel immersed in the liquid is shown.
- the relative fluorescence intensity is determined by calculating the brightness of the gel by image analysis.
- FIG. 15 shows the relationship between the relative fluorescence intensity obtained and the swelling ratio (volume change) of the EDANS-introduced BPA-responsive gel.
- the vertical axis represents the logarithm of relative fluorescence intensity (FZF), and the horizontal axis
- the optical property molecule-introduced stimulus-responsive gel according to the present invention is introduced with a molecule having a fluorescent chromophore or a molecule that absorbs visible light or ultraviolet light.
- the optical property molecule-introduced stimulus-responsive gel volume change can be converted into optical information as fluorescence intensity change or absorbance change, and used as a simple system when using the optical property molecule-introduced stimulus-responsive gel as a sensor element. be able to. Therefore, it can be applied to various purposes such as pollutant inspection in the environmental field and a new diagnostic system that can detect and measure biomolecules that are signals of diseases in the medical field. Therefore, the present invention can be used in various chemical industries such as the pharmaceutical manufacturing industry and the industrial chemical manufacturing industry, and further in the medical industry, and the strength is considered to be very useful.
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Abstract
Description
Claims
Priority Applications (3)
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EP06732267A EP1892519A4 (en) | 2005-04-28 | 2006-04-24 | STIMULI-SENSITIVE GEL WITH AN OPTICALLY CHARACTERISTIC MOLECULE INTRODUCED THEREIN, EXTERNAL STIMULI MEASURING APPARATUS USING THE SAME, AND METHOD OF MEASURING EXTERNAL STIMULI |
JP2007514713A JP5120808B2 (ja) | 2005-04-28 | 2006-04-24 | センサー素子およびこれを用いた外部刺激測定装置並びに外部刺激の測定方法 |
US11/919,133 US8999725B2 (en) | 2005-04-28 | 2006-04-24 | Method of measuring external stimulus and volume change using stimulus-responsive gel comprising EDANS |
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WO2008139902A1 (ja) * | 2007-05-07 | 2008-11-20 | Japan Science And Technology Agency | 分子応答性ゲル微粒子およびその製造方法ならびにその利用 |
WO2012117588A1 (ja) * | 2011-02-28 | 2012-09-07 | 独立行政法人科学技術振興機構 | 複数物質応答性ゲルおよびその製造方法並びにその利用 |
WO2018191403A1 (en) * | 2017-04-11 | 2018-10-18 | The Regents Of The University Of California | Materials for autonomous tracking, guiding, modulating, and harvesting of energetic emissions |
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WO2008084571A1 (ja) | 2007-01-12 | 2008-07-17 | Japan Science And Technology Agency | 核酸応答性ゲルおよびその製造方法ならびにその利用 |
US8477303B2 (en) | 2011-01-26 | 2013-07-02 | Hewlett-Packard Development Company, L.P. | Reconfigurable surface enhanced Raman spectroscopy apparatus, system and method |
US9080980B2 (en) | 2011-07-27 | 2015-07-14 | Hewlett-Packard Development Company, L.P. | Surface enhanced raman spectroscopy employing a nanorod in a surface indentation |
US11389105B2 (en) * | 2017-10-31 | 2022-07-19 | Brittany Molkenthin | Systems and methods for measuring a quantity of breast milk consumed by a baby |
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US20100063771A1 (en) | 2010-03-11 |
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