WO2020059707A1 - Procédé pour la réduction de géniposide, de génipine et d'un analogue de ceux-ci inclus dans des ingrédients qui contiennent du jaune de gardenia jasminoides - Google Patents

Procédé pour la réduction de géniposide, de génipine et d'un analogue de ceux-ci inclus dans des ingrédients qui contiennent du jaune de gardenia jasminoides Download PDF

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WO2020059707A1
WO2020059707A1 PCT/JP2019/036370 JP2019036370W WO2020059707A1 WO 2020059707 A1 WO2020059707 A1 WO 2020059707A1 JP 2019036370 W JP2019036370 W JP 2019036370W WO 2020059707 A1 WO2020059707 A1 WO 2020059707A1
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activated carbon
geniposide
gardenia yellow
genipin
analogs
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PCT/JP2019/036370
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English (en)
Japanese (ja)
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諒 石橋
剛 箕川
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三栄源エフ・エフ・アイ株式会社
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Publication of WO2020059707A1 publication Critical patent/WO2020059707A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B61/00—Dyes of natural origin prepared from natural sources, e.g. vegetable sources

Definitions

  • the present invention relates to a method for reducing geniposide, genipin and their analogs contained in a material containing gardenia yellow pigment.
  • gardenia blue pigment, gardenia red pigment, and gardenia yellow pigment, which are gardenia-derived pigments, have been used as food colorings.
  • gardenia yellow pigment is generally obtained by extracting fruits of gardenia gardenia (Gardenia augusta MERRILL var.grandiflora HORT., Gardenia jasminoides ELLIS) with water or hydrous ethanol.
  • the main pigment components of "gardenia yellow” are crocin and crocetin. Therefore, the "gardenia yellow dye” is not a single compound but usually contains geniposide derived from the raw material.
  • Patent Document 1 discloses that crocin, which is a pigment component of gardenia yellow, is selectively adsorbed to a specific synthetic adsorption resin, and geniposide, which causes greening of gardenia yellow, is used as a main component. Techniques for removing iridoid glycosides have been proposed. In addition, in the said patent document 1, since the activated carbon non-selectively adsorbs both the gardenia yellow pigment component and the geniposide, the activated carbon treatment separates the gardenia yellow pigment component and the geniposide. It states that you cannot do that.
  • Non-Patent Document 2 it is known that gardenia fruits contain a plurality of geniposide having an iridoid skeleton and analogs thereof.
  • Non-Patent Document 2 it has not been clarified whether the geniposide analog is contained in the extract containing the gardenia yellow pigment and the content ratio thereof.
  • an object of the present invention is to provide a new method for reducing geniposide, genipin and their analogs from a material containing gardenia yellow pigment.
  • a material containing a gardenia yellow dye contains geniposide and an analog thereof. Therefore, as a result of intensive studies on materials that can be used to reduce geniposide, genipin and their analogs from the materials, some types of activated carbon were found to contain materials containing gardenia yellow pigment (that is, gardenia yellow pigment).
  • a composition containing a pigment component and geniposide, genipin and their analogs and found to form cake-like lumps, and by treatment with activated carbon having such properties. It was found that geniposide, genipin and their analogs can be reduced while suppressing the loss of the pigment component of gardenia yellow pigment.
  • the present invention includes the following aspects.
  • a method for reducing at least one selected from the group consisting of geniposide, genipin, and analogs thereof contained in a material containing a gardenia yellow dye A method comprising treating with activated carbon which forms a cake-like mass by stirring and mixing with a gardenia yellow extract.
  • the activated carbon is used in an amount of 1 to 10% by mass with respect to a gardenia yellow extract.
  • a method for selecting activated carbon for reducing at least one selected from the group consisting of geniposide, genipin, and analogs thereof from a material containing gardenia yellow pigment A method for selecting activated carbon from which a cake-like mass is formed by stirring and mixing with a gardenia yellow extract.
  • a method for selecting activated carbon from which a cake-like mass is formed by stirring and mixing with a gardenia yellow extract A method for selecting activated carbon from which a cake-like mass is formed by stirring and mixing with a gardenia yellow extract.
  • a method for producing a gardenia yellow element composition wherein at least one selected from the group consisting of geniposide, genipin and analogs thereof is reduced, A step of contacting the activated carbon with a gardenia yellow element-containing material that forms cake-like lumps when brought into contact with the gardenia yellow element extract;
  • a method that includes [7] A method for producing a gardenia yellow element composition, wherein at least one selected from the group consisting of geniposide, genipin and analogs thereof is reduced, A step of selecting activated carbon that forms a cake-like mass when stirred and mixed with the gardenia yellow element extract; and a step of contact-treating the activated carbon selected in the selecting step with a material containing a gardenia yellow element;
  • a gardenia yellow element composition having a total content of geniposide, genipin and their analogs of not more than 35 ppm in terms of a color value of 100.
  • a gardenia yellow pigment composition obtained by the method according to any one of [6] to [8].
  • FIG. 2 (A) is a chromatogram (LC / MS) of the total ion fragments contained in the gardenia yellow dye-containing material.
  • FIG. 2 (B) is a chromatogram of ion fragments of gardenia yellow (upper) and iridoid analogs (lower) contained in a gardenia yellower containing material. The values of each chromatogram are comparable to each other.
  • the “color value” is “E 1 cm 10% ” unless otherwise specified.
  • the “color value” is determined according to the method described in the Ninth Edition Official Standards for Food Additives (Ministry of Health, Labor and Welfare).
  • “100 conversion of color value” means that various numerical values such as measured values are converted into numerical values per 100 color values of target materials, pigments, and the like.
  • the content of geniposide, genipin and their analogs contained in a material having a color value of 200 is 500 ppm
  • the content of geniposide, genipin and their analogs at a color value of 100 is 500 ppm
  • the content of the color value is 500 ppm.
  • the measured value of a sample having a color value of 100 can itself be a numerical value in “converted to a color value of 100”.
  • room temperature and “normal temperature” mean a temperature in the range of 10 to 40 ° C.
  • colorant component or “gardenia yellow component” means the essence of coloring (coloring principal).
  • the "gardenia yellow color composition” contains or consists of only a pigment component; it may contain components derived from raw materials other than the pigment component, components resulting from the production method, or both.
  • “Gardenia yellow element composition” refers to a pigment-containing composition after activated carbon treatment.
  • the “material containing gardenia yellow dye” refers to a dye-containing material containing a gardenia yellow dye derived from a natural product before activated carbon treatment.
  • the gardenia-yellow-containing material can be, for example, a gardenia nut extract.
  • the gardenia fruit extract includes a gardenia yellow crude extract extracted with an extraction solvent, a crude extract containing a solid, a dried product from the extract, a purified product thereof, and the like.
  • the gardenia-yellow-containing material may be a juice or dried juice of gardenia.
  • the gardenia-yellow-containing material may be a gardenia fruit (solid) or a crushed fruit.
  • the gardenia-yellow-containing material may be a gardenia extract or a gardenia-yellow preparation that is commercially available.
  • “Gardenia Yellow” is defined as follows in the Ninth Edition Official Addendum of Food Additives (Ministry of Health, Labor and Welfare of Japan). In the present specification, the “gardenia yellow pigment” can conform to the definition. Definition: "The product is based on crocin and crocetin, obtained from the fruits of the gardenia (Gardenia augusta Merrill or Gardenia jasminoides Ellis). It may contain dextrin or lactose.”
  • the method of the present invention for reducing geniposide, genipin and their analogs contained in gardenia yellow element-containing material is a method of stirring and mixing with a gardenia yellow element extract.
  • the method comprises a treatment using activated carbon, which forms a cake-like mass.
  • a gardenia yellow element-containing material is mixed in a 50 mL glass container by stirring 20 g of a gardenia yellow element extract (color value: 100) and 1 g of activated carbon at room temperature (10 to 40 ° C.) for 1 hour.
  • the method may be a method of reducing geniposide, genipin and their analogs by treating with activated carbon which forms cake-like lumps.
  • the "gardenia yellow pigment extract” refers to a liquid prepared to a color value of 100 from a material containing gardenia yellow pigment.
  • “reduction” means that the amounts of geniposide, genipin and their analogs in the object to be treated are reduced. That is, the “reduction” means that the amount of at least one selected from the group consisting of geniposide, genipin and their analogs in the object to be treated has been reduced as compared to before the treatment, and complete removal thereof However, it is not always necessary to remove all of them. In other words, even if geniposide, genipin and their analogs are not completely removed, it is applicable to the practice of the present invention, but geniposide, genipin and their analogs are completely or almost completely removed. Is preferred.
  • the gardenia yellow pigment is generally obtained by extracting the fruits of the gardenia gardenia with water or hydrous ethanol. Therefore, the gardenia-containing element usually contains geniposide and its analogs derived from the raw material.
  • Gardenia fruit contains various geniposide analogs, and the geniposide analog removed by the method of the present invention may be any compound having an iridoid skeleton (including glycosides). Examples include, but are not limited to, gardenate A, gardenamide, 6 ′′ -Op-cis-coumaroylgenipin gentiobioside, 7 ⁇ , 8 ⁇ -epoxy-8 ⁇ -dihydrogeniposide, and 8-epiapodantheroside.
  • Genipin is, for example, a substance produced by treating geniposide with ⁇ -glucosidase in a process of producing a gardenia blue pigment, and is not contained much in gardenia fruits.
  • genipin and its analogs are produced by treating geniposide and its analogs contained in gardenia fruit with ⁇ -glucosidase.
  • the amount of the ⁇ geniposide, genipin and their analogs '' in the ⁇ material containing gardenia yellow element '' when the reduction method of the present invention is applied is not particularly limited, and may be an amount for which the reduction is desired. I just need.
  • the lower limit of the total content of geniposide, genipin and their analogs in terms of color value 100 is 5 ppm, 10 ppm, 20 ppm, 25 ppm, 30 ppm, 40 ppm, It can be 50 ppm, 80 ppm, 100 ppm, 150 ppm, 200 ppm, 250 ppm, 300 ppm, 350 ppm, or 400 ppm.
  • the amount is in the range of 5 to 5000 ppm, in the range of 10 to 5000 ppm, in the range of 20 to 5000 ppm, and in the range of 25 to 5000 ppm as the total content of geniposide, genipin and their analogs in terms of color value 100.
  • the total content of geniposide, genipin and their analogs in terms of a color value of 100 is in the range of 5 to 1000 ppm, in the range of 10 to 900 ppm, in the range of 50 to 800 ppm, and in the range of 100 to 1000 ppm. Within the range, 200-800 ppm. In the case of gardenia yellow, the "total content of geniposide, genipin and their analogs" is usually equal to the content of geniposide and its analogs.
  • the amounts of geniposide, genipin and their analogs are determined by LC / MS analysis under the following conditions or an analysis method capable of obtaining an analysis result equivalent thereto, unless otherwise specified. .
  • LC / MS using all-ion fragmentation method (AIF method) is preferred.
  • AIF method all-ion fragmentation method
  • the analysis quantifies compounds having a common backbone (analogs).
  • analogs one by one by combining known methods such as NMR.Therefore, a standard product of the identified analog is prepared, and a standard curve method is applied to the sample. It is also possible to quantify the contained analogs.
  • the detection limit of geniposide is about 10 ppb, and the detection limit of genipin is about 100 ppb.
  • the color value of gardenia yellow is determined by the following color value measurement method.
  • ⁇ Method for measuring color value of gardenia yellow element A sample equivalent to about 5 g in terms of a color value of 100 was precisely weighed, 50 ml of a 0.02 mol / L sodium hydroxide solution was added to the sample, and the mixture was heated in a 50 ° C water bath for 20 minutes. If present, dissolve with shaking and add water to make exactly 100 ml. Measure exactly 1 ml, add 50 vol% ethanol to make exactly 100 ml, centrifuge if necessary, and use the supernatant as the test solution.
  • the material containing gardenia yellow pigment is not limited, but for example, a powder or liquid raw material can be diluted with water so as to have a color value of 100 and then subjected to an activated carbon treatment.
  • a commercially available liquid concentrate as a material containing gardenia yellow dye is diluted with water so as to have a color value of 100, and then subjected to activated carbon treatment.
  • a gardenia fruit extract (a gardenia yellow crude extract extracted with an extraction solvent, a crude extract containing a solid, a dried product from the extract, or a purified product thereof) may be used as it is or diluted. , May be subjected to activated carbon treatment.
  • the juice or dried juice of gardenia fruit may be used as it is or diluted and then subjected to activated carbon treatment. Further, gardenia fruits (solid) or crushed fruits may be contacted with activated carbon. Further, gardenia fruit (solid) or a crushed fruit may be brought into contact with activated carbon (solid) in a liquid.
  • the activated carbon used in the reduction method of the present invention is an activated carbon that forms a cake-like mass by stirring and mixing with the gardenia yellow extract.
  • 20 g of a gardenia yellow extract (color value 100) and 1 g of activated carbon are stirred and mixed at room temperature (10 to 40 ° C.) for 1 hour in a 50 mL glass container, and the mixture is stirred at room temperature (10 to 40 ° C.). After 2 hours, a cake-like mass is formed.
  • the 50 mL glass container is preferably a mighty vial manufactured by Maruem Corporation.
  • the normal temperature may be any of 10 to 40 ° C. as described above, but may be, for example, 25 ° C.
  • the stirring and mixing for one hour is preferably performed at 200 to 500 rpm.
  • the cake-like mass is, for example, in a 50-mL glass container, 20 g of gardenia yellow extract (color value 100) and 1 g of activated carbon are stirred and mixed for 1 hour, left to stand for 2 hours, and then decanted.
  • the lump remaining without changing its shape is shown on the glass bottom side.
  • the entire bottom surface of the glass container is covered with a cake of activated carbon, and the glass on the bottom surface is not exposed.
  • the residual amount of the glass container after decantation is preferably 3 g or less, more preferably 2 g or less.
  • the decantation condition refers to a step of removing only the supernatant while tilting the container. That is, in the present invention, at the time of decantation, the activated carbon used for the treatment is present as a lump, and the liquid is in a good drainage state.
  • the cake-like mass is preferably stirred and mixed with 20 g of gardenia yellow extract (color value: 100) and 1 g of activated carbon in a 50 mL glass container for 1 hour, and allowed to stand for 2 hours. It may have the property of remaining in the container after standing for 10 minutes at room temperature in the state of being inverted by 180 °.
  • the activated carbon that can be used in the present invention forms a cake-like mass when contacted with the gardenia yellow extract, and the activated carbon (decant) remaining after removing the extract after the contact is between the activated carbon particles.
  • the mass tends to increase as compared with activated carbon before use.
  • the removal efficiency of geniposide and the like tends to be inferior, so that it is preferably 110% or more, more preferably 120% or more, and further preferably It is at least 130%, even more preferably at least 140%, particularly preferably at least 150%, most preferably at least 160%.
  • the mass increase rate of the activated carbon when the mass increase rate of the activated carbon is more than 320%, the residual rate of the gardenia yellow pigment tends to be low. Therefore, it is preferably 320% or less, more preferably 310% or less, and still more preferably 300% or less. It is even more preferably at most 280%, particularly preferably at most 260%. Accordingly, the mass increase of the activated carbon that can be used in the present invention is, for example, 110% to 320%, preferably 110% to 300%, more preferably 110% to 280%, and further preferably 110% to 260%.
  • the mass increase rate can be determined by [(decant residual amount (wet weight, g)) / initial activated carbon amount (dry weight, g)] ⁇ 100 (%).
  • the mechanism for forming a cake-like mass when the activated carbon is brought into contact with the gardenia yellow extract is not particularly limited, but the dissociable functional groups present on the solid surface of the activated carbon and the activated carbon are formed through the activation process. It is considered that due to the difference in the surface functional groups, the surface charge of the activated carbon surface and the gardenia yellow element attract each other to cause aggregation. That is, the activated carbon that can be used in the present invention is aggregated by some components of the gardenia extract containing geniposide and the like, but the components of the gardenia yellow dye such as crocin are not considered to be involved in the reaction.
  • the activated carbon used in the present invention is not limited, but examples thereof include coconut shell, coal, wood flour and the like, and preferably coconut shell.
  • the activation method is also not particularly limited, but is preferably steam activation.
  • the particle diameter is not particularly limited, either.
  • the powder may preferably be 0.15 mm or less in diameter.
  • the treatment with activated carbon is carried out by bringing a material containing gardenia yellow color into contact with activated carbon.
  • the treatment with activated carbon can be performed in a glass, resin, or stainless steel container by a batch method.
  • the capacity of the container is not limited, for example, it can be performed in a container of 10 L or more, or 100 L or more, or 500 L or more.
  • geniposide, genipin and their analogs are adsorbed on the activated carbon.
  • geniposide, genipin and their analogs are removed by removing the activated carbon to which geniposide, genipin and their analogs are adsorbed.
  • Activated carbon that can be used in the present invention has a property of hardening into a cake by predetermined contact with a gardenia yellow element extract, so that a gardenia yellow element composition in which geniposide, genipin and their analogs are reduced, is used as a supernatant liquid. It becomes possible to collect efficiently and easily. That is, it is easy to separate the dye present in the liquid from geniposide, genipin and their analogs adsorbed on the activated carbon due to the good drainage of the liquid. Further, due to such properties of the activated carbon, an excellent effect that a residue of the activated carbon used in the treatment hardly remains in the gardenia yellow pigment composition is exhibited. Since the residue of the activated carbon hardly remains, clogging or the like by the activated carbon hardly occurs in the next purification operation or the like, and the efficiency of the process can be further improved.
  • Contacting the material containing gardenia yellow yellow with activated carbon is performed when the material is a water-soluble solid, for example, by dissolving or suspending the material in an aqueous or organic solvent to form a liquid, And the activated carbon can be mixed.
  • the material is a water-insoluble solid, for example, it can be carried out by mixing the material and activated carbon in a liquid, or by bringing a mixture of the material and activated carbon into contact with the liquid.
  • the extraction can be performed as it is or by diluting with an aqueous solvent or an organic solvent and mixing the material in the liquid state with activated carbon.
  • the mixing may be performed by a conventional means using a shaker, a stirrer, or the like.
  • the aqueous solvent include water (eg, tap water, ion-exchanged water, distilled water), and hydrated alcohol (eg, hydrated ethanol).
  • the organic solvent include lower alcohols (eg, methanol, ethanol, etc.).
  • the solvent is preferably an aqueous solvent, and the aqueous solvent is more preferably low in the content of alcohol (eg, ethanol), More preferably, it is water (eg, tap water, ion-exchanged water, distilled water).
  • the pH of the “material in a liquid state” is not particularly limited, but is usually in the range of 2.0 to 7.0, preferably 3.0 to 7.0, and more preferably 3.5 to 6. It is within the range of 0.
  • the adjustment may be performed by a conventional method such as using hydrochloric acid or sodium hydroxide.
  • the temperature of the treatment with activated carbon is not particularly limited, but may be usually performed at room temperature.
  • the suitable amount of activated carbon used in the treatment with activated carbon is not particularly limited, but is in the range of 0.1 to 10% by mass, more preferably 1 to 7% by mass, based on the extract. It is.
  • the amount of activated carbon is preferably based on the total amount of extract and activated carbon.
  • the range of 1 to 10% by mass more preferably in the range of 2 to 8% by mass, and still more preferably in the range of 3 to 7% by mass.
  • the preferred amount of the activated carbon used for the treatment with the activated carbon is, for example, the amount of the activated carbon per 1 part by mass (color value: 100) of the solution containing gardenia yellow dye, preferably 0.01 to 0.5 part by mass, more preferably Is 0.03 to 0.5 part by mass, more preferably 0.03 to 0.3 part by mass, still more preferably 0.03 to 0.1 part by mass, particularly preferably 0.05 to 0.3 part by mass. Parts, most preferably 0.05 to 0.1 parts by weight.
  • the time of the treatment with activated carbon is not particularly limited, but the contact time may preferably be a batch method in which the mixing time is 30 minutes or more and the standing time is 10 minutes or more.
  • the mixing time is preferably in the range of 30 minutes to 40 hours, more preferably 1 hour to 30 hours, and the standing time is preferably 10 minutes to 60 hours, more preferably 1 hour to 50 hours. Within the time range.
  • the “material containing gardenia yellow color” may have been previously subjected to an adsorption treatment, and then the “treatment with activated carbon” may be performed.
  • “geniposide, genipin and their analogs” can be removed by the treatment by the adsorption treatment.
  • the amount of activated carbon used in “treatment with activated carbon” can be reduced.
  • the adsorption treatment is not particularly limited, and examples thereof include an adsorption treatment using silica gel or a porous ceramic; and an adsorption treatment using a synthetic adsorption resin.
  • the adsorption treatment can be performed by either a batch method or a column method.
  • the adsorption condition is not particularly limited as long as the gardenia yellow dye is adsorbed on the above-mentioned adsorption resin, but the material containing the gardenia yellow dye is usually brought into liquid contact under conditions of pH 2 to 7, preferably pH 3 to 5. It is desirable.
  • the desorption of gardenia yellow pigment is obtained by washing the above resin with water and then passing it through with a lower organic alcohol such as ethanol or isopropanol or a hydrophilic organic solvent such as acetone or a mixture of these hydrophilic organic solvents and water as an eluent. You can do this by doing
  • geniposide analogs show physical properties (adsorbability) similar to crocin, which is a gardenia yellow component, when the adsorption treatment is performed, so that even if the adsorption treatment is performed, gardenia yellow remains.
  • crocin which is a gardenia yellow component
  • the amount of geniposide, genipin and their analogs in the material is reduced while suppressing the loss of useful components such as gardenia yellow pigment in the material. be able to.
  • the residual ratio in the total content of geniposide, genipin and their analogs is determined. , Preferably 30% or less, more preferably 20% or less, even more preferably 10% or less, particularly preferably 5% or less, more preferably 3% or less, still more preferably 1% or less, particularly preferably 0% or less. 0.5% or less, still more preferably 0.1% or less, and most preferably 0%.
  • the residual ratio of the dye component which is a useful component, (that is, the ratio of the content of the dye component after treatment to the content of the dye component before treatment by the reduction method of the present invention) is preferably 70% or more. It is particularly preferably at least 80%, more preferably at least 85%, most preferably at least 90%.
  • the “residual rate of the dye component” can be the “residual rate of the color value”.
  • any type of activated carbon can reduce geniposide, genipin and their analogs from a material containing a gardenia yellow component without reducing a gardenia yellow component. Not in translation.
  • the present invention also relates to a method for selecting an activated carbon which can be suitably used for reducing geniposide, genipin and their analogs from a gardenia-yellow-containing material.
  • a method for selecting activated carbon may be referred to as a method for selecting activated carbon of the present invention. That is, one embodiment of the present invention may include a step of selecting activated carbon that can be used in the reduction method of the present invention.
  • whether or not a cake-like mass is formed by stirring and mixing with a gardenia yellow extract is used as a criterion.
  • a gardenia yellow extract color value 100
  • 1 g of activated carbon are stirred and mixed at room temperature (10 to 40 ° C.) for 1 hour in a 50 mL glass container, and the mixture is stirred at room temperature (10 to 40 ° C.).
  • a cake-like mass is formed as a criterion. That is, when a cake-like mass is formed under the above conditions, such activated carbon can be suitably used to reduce geniposide, genipin and their analogs from a material containing gardenia yellow pigment.
  • Activated carbon Activated carbon.
  • the room temperature may be any of 10 to 40 ° C as described above, but may be, for example, 25 ° C.
  • the stirring and mixing for one hour is preferably performed at 200 to 500 rpm.
  • the cake-like mass is preferably stirred and mixed in a 50 mL glass container with 20 g of gardenia yellow extract (color value 100) and 1 g of activated carbon, left for 2 hours, and then decanted. And lump remaining on the glass bottom side without changing its shape.
  • the entire bottom surface of the glass container is covered with a cake of activated carbon, and the glass on the bottom surface is not exposed.
  • the amount of the residue in the glass container after decantation is preferably 3 g or less, more preferably 2 g or less.
  • the decantation condition refers to a step of removing only the supernatant while tilting the container. That is, in the present invention, at the time of decantation, the activated carbon used for the treatment is present as a lump, and the liquid is in a good drainage state.
  • the cake-like mass is preferably stirred and mixed with 20 g of gardenia yellow extract (color value: 100) and 1 g of activated carbon in a 50 mL glass container for 1 hour, and allowed to stand for 2 hours. It may have the property of remaining in the container after standing for 10 minutes at room temperature in the state of being inverted by 180 °.
  • the present invention provides a method for selecting activated carbon for reducing geniposide, genipin, and their analogs from a material containing gardenia yellow element, and including a gardenia yellow element extract (with a color value of 100) in a 50 mL glass container.
  • 20 g and activated carbon 1 g were mixed under stirring at room temperature (10 to 40 ° C) for 1 hour, and allowed to stand at room temperature (10 to 40 ° C) for 2 hours.
  • the method may be a selection method including a step of determining whether or not to perform the determination.
  • 20 g of gardenia yellow extract (color value 100) and 1 g of activated carbon are stirred and mixed at room temperature (10 to 40 ° C.) for 1 hour in a 50-mL glass container, and then mixed at room temperature (10 to 40 ° C.). After standing at 40 ° C.) for 2 hours to determine whether or not cake-like lumps are formed; and, using activated carbon which forms cake-like lumps, contains gardenia yellow element Reducing the total content of geniposide, genipin and their analogs from a material containing gardenia yellow pigment, comprising the step of reducing geniposide, genipin and their analogs from the material.
  • geniposide, genipin and genipin are reduced by reducing geniposide, genipin and their analogs from a material containing gardenia yellow pigment containing genipin and their analogs.
  • a gardenia yellow element composition having a reduced total content of analogs thereof is a method for producing a gardenia yellow element composition in which the total content of geniposide, genipin, and their analogs is reduced.
  • the activated carbon that can be used in the method for producing a gardenia yellow dye composition is the same as the activated carbon that can be used in a method for reducing the total content of geniposide, genipin, and their analogs from a material containing a gardenia yellow dye. Accordingly, the method for producing the gardenia yellow element composition may include a step of selecting usable activated carbon.
  • ⁇ reduced '' means that the total content of geniposide, genipin and their analogs is lower than that of the starting material containing gardenia yellow color, and geniposide, genipin and their analogs are Substantially no content and no content are included.
  • the solution after the treatment with the activated carbon may be subjected to a conventional purification treatment (eg, a filtration treatment, a resin treatment, a membrane treatment, etc.).
  • a conventional purification treatment eg, a filtration treatment, a resin treatment, a membrane treatment, etc.
  • the gardenia yellow color composition obtained by the production method of the present invention may be in the form of a solution after treatment with activated carbon, in the form of its concentrate, or dried by any method (eg, vacuum drying, freeze drying, (Eg, spray drying).
  • the amount of ⁇ geniposide, genipin and their analogs '' contained in the gardenia yellow pigment composition obtained by the production method of the present invention is preferably, as a total content of geniposide, genipin and their analogs, in terms of a color value of 100, Is 35 ppm or less, more preferably 30 ppm or less, still more preferably 25 ppm or less, still more preferably 10 ppm or less, particularly preferably 5 ppm or less, more particularly preferably 3.5 ppm or less, still more preferably 2 ppm or less, and still more preferably It can be 1 ppm or less, most preferably 0.5 ppm or less.
  • the lower limit of the amount is not limited, for example, the gardenia yellow element composition in which the amount is 0.1 ppm or more, 0.3 ppm or more, 0.5 ppm or more, 1 ppm or more, 2 ppm or more, or 5 ppm or more is used. May be acceptable depending on the purpose and form of the
  • the total content of geniposide, genipin and their analogs in terms of a color value of 300 is 100 ppm or less (more preferably, 80 ppm or less, still more preferably 50 ppm or less, still more preferably 20 ppm or less, and particularly preferably. Is 10 ppm or less, more preferably 5 ppm or less, still more preferably 3 ppm or less, still more preferably 1 ppm or less, and most preferably 0 ppm (or below the detection limit in the above-mentioned measurement method).
  • a gardenia yellow pigment composition can be obtained by the production method of the present invention described above.
  • the amount of "geniposide and / or genipin" contained in the gardenia yellow color composition obtained by the production method of the present invention is preferably 35 ppm or less, as a total content of geniposide and genipin in terms of a color value of 100, More preferably 30 ppm or less, further preferably 25 ppm or less, still more preferably 10 ppm or less, particularly preferably 5 ppm or less, more particularly preferably 3.5 ppm or less, still more preferably 2 ppm or less, particularly still more preferably 1 ppm or less, and most preferably.
  • the lower limit of the amount is not limited, for example, the gardenia yellow element composition in which the amount is 0.1 ppm or more, 0.3 ppm or more, 0.5 ppm or more, 1 ppm or more, 2 ppm or more, or 5 ppm or more is used. May be acceptable depending on the purpose and form of the
  • One embodiment of the present invention has a total content of geniposide and genipin of 100 ppm or less (more preferably, 80 ppm or less, further preferably 50 ppm or less, still more preferably 20 ppm or less, particularly preferably 10 ppm or less, in terms of a color value of 300. It is particularly preferably at most 5 ppm, more preferably at most 3 ppm, particularly preferably at most 1 ppm, most preferably at 0 ppm (or below the detection limit in the above-mentioned measuring method).
  • a gardenia yellow pigment composition can be obtained by the production method of the present invention described above.
  • the gardenia yellow dye composition obtained by the production method of the present invention can be used in the same manner as a conventional gardenia yellow dye composition, and can be provided as it is as a pigment preparation. Furthermore, a diluent, a carrier or other additives may be added to the gardenia yellow pigment composition as other components, and the composition may be provided as a pigment preparation in that state.
  • diluents those generally used in dye preparations, particularly water-soluble dye preparations, can be widely used as long as the effects of the present invention are not impaired.
  • examples include sucrose, lactose, glucose, dextrin, gum arabic, water, ethanol, propylene glycol, glycerin, starch syrup, and the like.
  • the form of the pigment preparation is not particularly limited, and may be prepared in any form such as powder, granule, tablet, liquid, emulsion, or paste.
  • the gardenia yellow dye composition of the present invention or a pigment preparation containing the same can be widely used as a coloring agent for foods, cosmetics, pharmaceuticals, quasi-drugs, feeds, etc., similarly to the conventional gardenia yellow dye color composition or preparation.
  • the present invention provides a colored composition of food, cosmetics, pharmaceuticals, quasi-drugs, feed, and the like, which is colored using the gardenia yellow pigment composition or a pigment preparation thereof.
  • the food include confectionery such as frozen dessert, raw confectionery, Japanese confectionery, and western confectionery; beverages such as beverages and alcoholic beverages; processed agricultural products such as dried vegetables and pickles; processed marine products; Include.
  • the cosmetics include cosmetics (eg, eye shadow, mascara, lipstick, lip balm, and lotion), soaps, shampoos, rinses, detergents, toothpastes, mouthwashes, and the like.
  • the drug include tablets (eg, sugar-coated tablets), granules, solutions, capsules, and the like.
  • the content of the gardenia yellow pigment in these coloring compositions is not particularly limited, but is about 410 to 425 nm, and is such an amount that the absorbance of the coloring composition at its maximum absorption wavelength becomes 0.01 to 1. be able to.
  • MS / MS measurement in which the collision energy is changed and the decomposition treatment is performed three or more times is possible, and the compound ions after the decomposition treatment in the collision energy are electrically captured.
  • a mass spectrometer capable of detecting and integrating, or detecting and integrating can be used.
  • the apparatus described above i) disperses the compound ions after each decomposition treatment into a certain space during the three or more decomposition treatments in which the collision energy is changed. It is preferable that the mass spectrometer be capable of electronically supplementing and accumulating and accumulating it within the range, and integrating and detecting the same at once after completion of all the decomposition processes.
  • the above-mentioned apparatus may adopt a mode in which ii) the compound ions after the decomposition treatment are detected first, and this is repeated for the set amount of the collision energy, and then the detected values are integrated afterwards.
  • a known or unknown device or instrument can be appropriately used as long as it is a mass spectrometer capable of performing the above analysis.
  • a mass spectrometer based on an electric field Fourier transform method, a magnetic field Fourier transform method, an ion trap method, or the like can be used.
  • a mass spectrometer based on the electric field Fourier transform method examples include, at the time of the present application, a mass spectrometer based on the Orbitrap method manufactured by Thermo Fisher Scientific Co., Ltd.
  • the embodiments of the present invention are not limited to the embodiments using the above device.
  • the device be capable of LC / MS measurement in the analysis before the MS / MS measurement. That is, the device that can be used for quantification and analysis in the present invention is a device that utilizes the above principle, and is preferably a device that can perform LC / MS / MS measurement.
  • the analyzer provided with a quadrupole-type MS measuring means or the like as an analytical instrument before the MS / MS measurement.
  • quantification and analysis can be performed using AIF analysis using a mass spectrometer using the above principle.
  • AIF All Ion Fragmentation analysis
  • MS / MS measurement involving a plurality of decomposition treatments in which a target compound is changed in collision energy, and integrating the fragmented compound ions.
  • the measurement sample containing the target compound is subjected to decomposition treatment with the collision energy changed three times or more, and the fragmented compound ions are integrated. And acquiring a mass spectrum in the MS / MS measurement.
  • the MS / MS measurement in the AIF analysis step the peak ions of the mass spectrum obtained in the first MS measurement are decomposed and generated by giving energy (collision energy) for decomposition processing to detect compound ions.
  • the first MS measurement is a mass spectrometry process for acquiring a mass spectrum in which an undecomposed compound contained in a measurement sample is directly detected.
  • the MS / MS measurement is a second mass spectrometry step for fragmenting and detecting the peak ion of the first MS measurement.
  • the first MS measurement performed before the MS / MS measurement it is preferable that the first MS measurement be obtained as full MS scan data in order to comprehensively quantify a low-content target compound.
  • the first MS measurement it is preferable that the first MS measurement be obtained as full MS scan data in order to comprehensively quantify a low-content target compound.
  • the first MS measurement it is necessary to narrow down and select compounds having a desired molecular weight range to some extent, and then execute the MS / MS measurement. Is preferred.
  • the m / z value is preferably 100 to 2000, preferably 100 to 2000, as the target compound for the first MS measurement. It is preferable to obtain the first MS scan data by narrowing down the range of the molecular weight of the m / z value to about 100 to 1500.
  • the MS / MS measurement in the above analysis step ii) in the first MS measurement, full MS scan data for all compounds is obtained without limiting the molecular weight range, and the subsequent MS measurement is performed.
  • a mode in which the MS / MS measurement is narrowed down to a signal peak equal to or higher than a certain threshold value and / or a signal peak in an upper predetermined range may be adopted.
  • the quantification and analysis in the present invention do not exclude the embodiment described in the above ii), however, in the above embodiment, there is a risk that a compound having a small content in the sample leaks.
  • the first MS measurement in the analysis step is preferably an LC / MS measurement because the analysis target is a compound in a liquid sample.
  • the quantitative AIF analysis step of the present invention includes a step of performing MS / MS measurement by a decomposition treatment with a different collision energy for each of the peak ions constituting the first MS mass spectrum.
  • the MS / MS measurement is performed exhaustively in the above-described embodiment (i), and is performed in a data-dependent manner in the embodiment (ii).
  • HCD collision cell high energy collision dissociation cell
  • the quantification and analysis according to the present invention when a dye composition or the like extracted from a natural raw material composed of an enormous number of similar compounds having different molecular weights and structures is used as a measurement sample, three times or more in the MS / MS measurement described above.
  • the decomposition processing it is desirable to independently perform energy application and the like in each decomposition processing on the measurement sample in three or more times.
  • “independently three or more times” refers to an embodiment in which three or more separate decomposition processes are separately performed on the target sample.
  • the number of times of performing the decomposition treatment in the quantification and analysis in the present invention may be three or more times in order to cover the existence of similar compounds having different energy states required for decomposition in the sample. Specifically, about 3 to 20 times can be given.
  • (Condition 1) at least one of the decomposition processes is performed with low energy collision energy including an undecomposed peak of the target compound.
  • the collision energy of the above (condition 1) is an energy condition for recovering a target fragment ion derived from a low molecular target compound without excessive decomposition.
  • the collision energy is preferably a collision energy that includes the undecomposed peak of the target compound and also includes the peak of the fragment ion having the common structure.
  • At least another one of the decomposition processes substantially includes the undecomposed peak of the target compound and the peak of the fragment ion having the common structure. It is preferable to carry out the process with high energy collision energy.
  • the collision energy of the above (condition 2) is an energy condition for giving sufficient energy for the decomposition of the polymer target compound and recovering the target fragment ion derived from the polymer compound.
  • condition 2 “substantially not containing the undecomposed peak of the target compound” described in the above (condition 2) indicates a state in which the target compound as the measurement sample is sufficiently decomposed, and This shows a sufficient condition that the target fragment ion is decomposed and generated to such an extent that the quantitative property is ensured. Specifically, if the amount of the target compound in the undecomposed state before collision energy application is 10% or less, preferably 5% or less, more preferably 1% or less, it can be determined that the above condition is satisfied. . The determination as to whether or not an undecomposed peak of the target compound under the above conditions is included, it is possible to determine whether or not the target compound contained in the target dye composition or the like has the highest molecular weight as an index. Become.
  • condition 2 including a fragment ion peak is preferably 1% or more, preferably 5% or more, more preferably 10% with respect to the highest peak area of the fragment ion. With the above peak area, it can be determined that the above condition is clearly satisfied. If the peak area is too small, the target fragment ions may be excessively decomposed excessively, which is not preferable.
  • (condition 3) at least another one is performed at an energy between the two collision energies.
  • the collision energy of the decomposition process described in (condition 3) it is preferable that the energy state is different from that of the collision energy in another decomposition process.
  • the total number of decomposition processes in the MS / MS measurement is four or more, it is preferable that the above-mentioned (condition 3) the decomposition process using collision energy is performed a plurality of times.
  • the intervals of energy values between the respective decomposition treatments are evenly or substantially equal. It is preferable to employ a collision energy that makes it even.
  • “substantially equivalent” under the above conditions means that the error is within 10%, preferably within 5%, more preferably within 1%, and the target fragment ion is sufficient to ensure the quantitativeness of the present invention. It indicates the range that is decomposed and generated.
  • the collision energies in all the decomposition processing have different energy states from each other. It should be noted that an aspect in which overlapping decomposition processes are performed using collision energy in the same energy state is not excluded.
  • the order of the energy states of the collision energy in the plurality of decomposition processes is not particularly limited, and the decomposition processes can be performed in any order.
  • a wide and appropriate range of collision energy setting range It is preferable to set the range.
  • the setting range of the collision energy in the AIF analysis is not appropriate, the target compound in the measurement sample cannot be accurately quantified, which is not preferable.
  • the quantification and analysis according to the present invention when the setting range of the collision energy for a predetermined sample is examined by a predetermined apparatus, when the quantification for the same kind of sample is performed thereafter, the collision determined in the previous examination is determined.
  • the energy setting range By using the energy setting range, the quantitative operation can be performed quickly.
  • the above-mentioned AIF analysis step includes a step of obtaining a mass spectrum by MS / MS measurement including the integration of the fragmented compound ions after performing the decomposition treatment with the collision energy changed three times or more as described above. .
  • a mode of performing the integration of the compound ions after the decomposition treatment it is preferable to perform i) a mode in which the compound ions after the decomposition process by the collision energy are electrically supplemented and integrated for detection.
  • various fragmented compound ions including compound ions that remain undecomposed depending on the energy state
  • the compound in the sample is firstly subjected to the decomposition treatment by the collision energy of a certain intensity, and the compound ion obtained by the above treatment is obtained. (Including undecomposed compound ions and fragmented fragment ions, etc.) is electrically captured and accumulated in another space, (second time), and then collision energy of a different intensity from the first time is used.
  • the compound in the sample is subjected to decomposition treatment, and the compound ions obtained in the above treatment are electrically captured and accumulated in the space together with the compound ions in the previous stage (the 3rd to nth times).
  • N is an integer of 4 or more
  • the electrical capture state of the compound ions in the above process is different from the site where the decomposition processing by collision energy is performed in a mass spectrometer based on an electric field Fourier transform method, a magnetic field Fourier transform method, an ion trap method, or the like. It can be realized in a space or the like in which the electrodes are arranged.
  • an electrode arrangement space capable of supplementing and holding by rotating ions in an electric field around the electrode is provided.
  • Separately arranged collision energy decomposition reaction space is arranged, compound ions treated in the collision energy decomposition reaction space are sequentially flowed into the electrode installation space, and compound ions are sequentially captured in the electric field around the electrode.
  • a mode of accumulatively accumulating can be suitably exemplified.
  • the above aspect is particularly suitable for performing precise quantification, and can be realized in a mass spectrometer based on the electric field Fourier transform method or the like.
  • an electric field generated around the spindle electrode of the orbitrap MS2 in an apparatus utilizing the principle of the orbitrap method may be used.
  • the step of obtaining a mass spectrum in MS / MS measurement including the integrated fragmented compound ions in the AIF analysis step includes the step of integrating compound ions after the decomposition treatment as described in the above paragraph.
  • a mode in which the compound ions after the decomposition treatment are detected first, and this is repeated for the set amount of the collision energy, and then the data processing of integrating the detected values afterwards is adopted.
  • the above-mentioned embodiment ii) is not excluded from the scope of the present invention, however, in the present invention, the embodiment of i) described in the above paragraph is employed from the viewpoints of both analytical accuracy and simplicity of analytical operation. Is more preferred.
  • values obtained by performing various arithmetic processes can be used as the value indicating the integrated compound ion.
  • a value obtained by dividing by the number of times of performing the decomposition process and equalizing can be used for the above quantification.
  • the undecomposed target compound ion, the intermediate product ion, and the common structure which constituted the target compound were determined according to the degree of progress of the decomposition.
  • Various compound ions such as ions and excessively decomposed low molecular compound ions are included as integrated peak values at various stages of the degree of decomposition.
  • the target having the common structure contained in the measurement sample is used.
  • the total amount of the compound can be quantified or analyzed.
  • the AIF analysis step in the present invention includes a step of quantifying or analyzing the target compound from the mass spectrum obtained by the MS / MS measurement, using the common structure contained in the target compound as the target fragment ion as an index. .
  • the target component in view of the accurate quantification of the target component, it is a common structure possessed by the molecular species of the target compound in the measurement sample and not a constituent structure of the compound in the measurement sample other than the target compound. It is preferable to employ a compound ion.
  • the aglycone of the target compound contained in the measurement sample or a similar compound derived therefrom As the compound generated after the decomposition treatment that satisfies such conditions, it is preferable to employ the aglycone of the target compound contained in the measurement sample or a similar compound derived therefrom. That is, as the target fragment ion in the present invention, it is preferable that an aglycone ion of the target compound or a similar compound ion derived from the aglycon be a detection target.
  • examples of the ion of the analogous compound derived from aglycone include a functional group-substituted compound generated by a change in metabolism in a plant, storage or processing of a measurement sample, or the like.
  • concentration conversion In order to calculate the actual concentration value from the detection data of the target fragment ion having the common structure in the quantification in the present invention, one or more compounds containing the target fragment structure are prepared and a dilution series of the compound is prepared. The concentration value can be calculated from the detection data of the measurement sample only by creating the calibration curve.
  • a known curve containing the aglycone is analyzed under the same conditions as the AIF method of the present invention (setting collision energy, etc.) to create a calibration curve. From the detection data and molecular weight information of the measurement sample, the concentration value and the content value of the target compound in the measurement sample can be calculated.
  • aglycone is used as a target fragment
  • Any compound can be used as long as it can generate a common structural compound which is a target fragment, such as a known low-molecular-weight target compound containing the aglycone or a chloride of the aglycone.
  • the total amount of the target compound containing the aglycone as a “common structure” is determined by detecting aglycone constituting the target compound contained in the measurement sample as a target fragment ion in the AIF analysis. Becomes possible.
  • the common structure used as the target fragment ion may be, for example, an ion of an aglycone of geniposide (an glycoside of iridoid) or an ion of a similar compound derived from the aglycone.
  • the “total amount of all target compounds” contained in the measurement sample can be quantified using the AIF analysis.
  • the total amount of all target compounds can be quantified.
  • crocetin-based yellow dye components are determined by the AIF analysis using crocetin ion as a target fragment ion. Crocetin glycoside) can be determined and the above value can be used as the total amount of all crocetin-based yellow component contained in gardenia yellow component.
  • a measurement sample can also be suitably used for a dye composition or the like containing two or more target compounds of different types of aglycone.
  • the quantification according to the present invention it is possible to quantify the “individual component amount of each target compound” contained in the measurement sample by using the AIF analysis. Specifically, the aglycone constituting the desired target compound contained in the measurement sample is quantified as the target fragment ion by the AIF method of the present invention, and the signal content derived from the desired individual component is measured, whereby the measurement sample is measured. It is possible to quantify the individual content of the desired target compound in the above.
  • the individual component to be measured is prepared as a standard compound. It is not necessary to perform an operation for creating a calibration curve for each standard compound.
  • the quantification based on the above-described common structure can be performed, and at the same time, the structure of the individual components of the desired target compound contained in the measurement sample can be determined.
  • ordinary MS scan data is also acquired before the AIF analysis is performed. From the mass spectrum of the MS scan data, the fragmentation mass spectrum in the MS / MS measurement, etc.
  • the structure of the desired target compound can be determined by the functions normally provided in the device described in (1). In the above structural analysis, it may be effective to perform a multi-stage analysis by (MS) n-stage analysis (where n is a natural number) as necessary.
  • the present invention includes the following aspects. ⁇ 1> A method for reducing geniposide, genipin, and their analogs contained in a gardenia yellow element-containing material, A method for reducing geniposide, genipin and their analogs, comprising a step of contact-treating a material containing gardenia yellow color with activated carbon satisfying the following conditions: In a 50 mL glass container, 20 g of gardenia yellow extract (color value 100) and 1 g of activated carbon were stirred and mixed at room temperature for 1 hour, and allowed to stand at room temperature for 2 hours, after which a cake-like mass was formed. Activated carbon.
  • ⁇ 2> A method for reducing geniposide, genipin, and their analogs contained in the gardenia yellow element-containing material according to ⁇ 1>, The cake-like mass remains in the container after being left standing at room temperature for 10 minutes in a state where the glass container is inverted by 180 °, and the mass increase rate of the remaining activated carbon is 300% or less. Is the way.
  • a method for reducing geniposide, genipin, and their analogs contained in a gardenia yellow element-containing material according to ⁇ 1> The step of contacting the material containing gardenia yellow color with activated carbon is carried out in such a manner that the activated carbon is used in an amount of 0.01 to 0.5 parts by mass per 1 part by mass of the dye (color value 100), the contact time is 30 minutes or more, and the standing time Is performed in a batch process for 10 minutes or more.
  • a method for selecting activated charcoal for reducing geniposide, genipin and their analogs from a material containing a gardenia yellow dye wherein a material containing a gardenia yellow dye is placed in a 50 mL glass container and then 20 g of the extract (color value: 100) and 1 g of activated carbon were stirred and mixed at room temperature (10 to 40 ° C.) for 1 hour, and allowed to stand at room temperature (10 to 40 ° C.) for 2 hours.
  • a method of selecting, comprising determining whether a lump is formed.
  • ⁇ 5> The selection method according to ⁇ 4>, wherein The cake-like mass remains in the container after being left standing at room temperature for 10 minutes in a state where the glass container is inverted by 180 °, and the mass increase rate of the remaining activated carbon is 300% or less. Is the way.
  • ⁇ 6> A method for reducing geniposide, genipin, and their analogs contained in a gardenia yellow element-containing material, In a 50 mL glass container, 20 g of gardenia yellow extract (color value 100) and 1 g of activated carbon were stirred and mixed at room temperature (10 to 40 ° C.) for 1 hour, and mixed at room temperature (10 to 40 ° C.) for 2 hours.
  • a method that includes ⁇ 7> A method for reducing geniposide, genipin, and their analogs contained in the gardenia yellow element-containing material according to ⁇ 6>,
  • the step of contact-treating the activated carbon with a material containing a gardenia yellow element comprises: 0.01 to 0.5 parts by mass of activated carbon per 1 part by mass of a dye (color value: 100); a contact time of 30 minutes or more; A method wherein the process is performed in a batch process for a time of 10 minutes or more.
  • a gardenia yellow pigment composition having a total content of geniposide and genipin of 35 ppm or less in terms of a color value of 100.
  • a gardenia yellow pigment composition obtained by a method for reducing geniposide, genipin and their analogs contained in a gardenia yellow element-containing material, Gardenia yellow pigment composition, which is a method for reducing geniposide, genipin and their analogs, comprising a step of contact-treating a gardenia yellow element-containing material with an activated carbon satisfying the following conditions: In a 50 mL glass container, 20 g of gardenia yellow extract (color value: 100) and 1 g of activated carbon were stirred and mixed at room temperature for 1 hour, and allowed to stand at room temperature for 2 hours, after which a cake-like mass was formed.
  • a method for producing a gardenia yellow element composition comprising a step of contacting a material containing a gardenia yellow element with an activated carbon satisfying the following conditions: In a 50 mL glass container, 20 g of gardenia yellow extract (color value 100) and 1 g of activated carbon were stirred and mixed at room temperature for 1 hour, and allowed to stand at room temperature for 2 hours, after which a cake-like mass was formed.
  • the step of contacting the gardenia yellow element-containing material with activated carbon comprises: 0.01 to 0.5 parts by mass of activated carbon with respect to 1 part by mass of the dye (color value 100); a contact time of 30 minutes or more; It is performed by a batch method in which the standing time is 10 minutes or more.
  • iridoid analogs total content of geniposide, genipin and their analogs
  • Residual rate of iridoid analog (%) (amount of geniposide after treatment + amount of geniposide after treatment + amount of geniposide analog after treatment) / (amount of geniposide before treatment + amount of geniposide before treatment + amount of geniposide analog before treatment) ⁇ 100
  • the glass vial after decantation was allowed to stand still for 10 minutes in a state where it was inverted by 180 °, and the mass of activated carbon remaining in the vial (remaining amount of decant) was measured.
  • the activated carbons of Examples 1-4 were placed in a 50 ml glass vial in 20 ml of gardenia yellow extract with a color value of 100 and 1 g of activated carbon (5% (w / w / gardenia yellow extract). The mixture obtained in w)) was stirred at 300 rpm for 1 hour and allowed to stand at room temperature for 2 hours, so that the activated carbon became a cake. Thereafter, decantation was performed and the supernatant was recovered. When these activated carbons were used, the gardenia yellow pigment could be easily separated.
  • the activated carbon of the comparative example which did not become cake-like fell with decantation, and the operability was not good.
  • the activated carbon of the comparative example when the glass bottle is inverted by 180 °, the activated carbon falls down partly or entirely, and it is expected that the actual operation when processing a large amount of samples becomes difficult.
  • the decant remaining amount of the activated carbons of Examples 1 to 4 in which geniposide was well adsorbed was smaller than the decanting amount of the activated carbons of Comparative Examples 1 to 4 in which almost no geniposide was adsorbed.
  • the goodness of the drainage of the activated carbon of Examples 1 to 4 which was in the form of a cake was remarkable.
  • Test example 2 Analysis of Geniposide Analogs Contained in gardenia Yellow Element-Containing Materials
  • bioactive components contained in gardenia yellow element genipin and geniposide are known, but have an iridoid skeleton and are close to gardenin yellow element components Since a polar geniposide analog may have been present, a gardenia yellow extract extracted to a color value of 5 with ultrapure water was used as a sample, and the orbitrap method (AIF method) was used for the sample. The contained geniposide analogs were subjected to LC / MS analysis.
  • Test example 3 Removal test of geniposide and its analogs from a material containing gardenia yellow color using activated carbon From the results of Test Example 2, it was found that a material containing a gardenia yellow color contains analogs having an iridoid skeleton other than geniposide. For this reason, a sample prepared in the same manner as in Test Example 1 was used to evaluate the effect of removing activated iridoid analogs by activated carbon treatment. In this test, the activated carbon of Example 1 having the highest effect of reducing geniposide was used and analyzed under the same conditions as in Test Example 2.
  • the activated carbon used in the examples can be efficiently used in a method for reducing geniposide, genipin, and their analogs contained in a gardenia yellow matter-containing material, and can be used for processing a sample on a larger scale. Can be used.

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  • Organic Chemistry (AREA)
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Abstract

La présente invention a pour objet un procédé pour la réduction de géniposide, de génipine et d'un analogue de ceux-ci inclus dans des ingrédients qui contiennent du jaune de Gardenia jasminoides. Comme procédé pour la réduction de géniposide, de génipine et d'un analogue de ceux-ci contenus dans des ingrédients qui contiennent du jaune de Gardenia jasminoides, la présente invention concerne un procédé pour la réduction de géniposide, de génipine et d'un analogue de ceux-ci, le procédé comprenant une étape consistant à traiter un ingrédient qui contient du jaune de Gardenia jasminoides avec un charbon actif ce qui forme une masse en forme de gâteau par agitation et mélange de l'ingrédient avec un extrait de jaune de Gardenia jasminoides.
PCT/JP2019/036370 2018-09-18 2019-09-17 Procédé pour la réduction de géniposide, de génipine et d'un analogue de ceux-ci inclus dans des ingrédients qui contiennent du jaune de gardenia jasminoides WO2020059707A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5486668A (en) * 1977-12-15 1979-07-10 Taito Kk Production of red type color composition
JPS57151657A (en) * 1981-03-13 1982-09-18 Riken Vitamin Co Ltd Preparation of yellow pigment resistant to green discoloration
CN105315705A (zh) * 2015-11-12 2016-02-10 江西省林业科学院 栀子中提取纯化栀子黄色素的方法
WO2016068330A1 (fr) * 2014-10-30 2016-05-06 三栄源エフ・エフ・アイ株式会社 Procédé d'élimination de géniposide et/ou de génipine

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5486668A (en) * 1977-12-15 1979-07-10 Taito Kk Production of red type color composition
JPS57151657A (en) * 1981-03-13 1982-09-18 Riken Vitamin Co Ltd Preparation of yellow pigment resistant to green discoloration
WO2016068330A1 (fr) * 2014-10-30 2016-05-06 三栄源エフ・エフ・アイ株式会社 Procédé d'élimination de géniposide et/ou de génipine
CN105315705A (zh) * 2015-11-12 2016-02-10 江西省林业科学院 栀子中提取纯化栀子黄色素的方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
XU, W. ET AL.: "Selective extraction of gardenia yellow and geniposide from Gardenia jasminoides by mechanochemistry", MOLECULES, vol. 21, no. 5, 2016, pages 1 - 13, XP055693920 *

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