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WO2024257383A1 - Procédé d'isomérisation de caroténoïde - Google Patents

Procédé d'isomérisation de caroténoïde Download PDF

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Publication number
WO2024257383A1
WO2024257383A1 PCT/JP2024/002069 JP2024002069W WO2024257383A1 WO 2024257383 A1 WO2024257383 A1 WO 2024257383A1 JP 2024002069 W JP2024002069 W JP 2024002069W WO 2024257383 A1 WO2024257383 A1 WO 2024257383A1
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Prior art keywords
trans
carotenoids
cis
carotenoid
oils
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PCT/JP2024/002069
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English (en)
Japanese (ja)
Inventor
大澤 友紀子 鈴木
真己 本田
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Eneos Materials Corp
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Eneos Materials Corp
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Publication of WO2024257383A1 publication Critical patent/WO2024257383A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/703—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups
    • C07C49/743—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups having unsaturation outside the rings, e.g. humulones, lupulones

Definitions

  • the present invention relates to a method for isomerizing trans-carotenoids to cis-carotenoids.
  • Carotenoids are natural pigments that are widely found in nature. Known types of carotenoids include astaxanthin, adonirubin, adonixanthin, zeaxanthin, and ⁇ -cryptoxanthin. These carotenoids are known to have various physiological effects. Cis-carotenoids are more easily absorbed by the body than trans-carotenoids, and are expected to have better effects than trans-carotenoids, so they are expected to be used in foods, medicines, etc.
  • Patent Document 1 describes a primary composition in which a specific cis isomer is enriched by subjecting a carotenoid composition containing lycopene to heat treatment, microwave irradiation, or the like, and a method for producing the primary composition.
  • Patent Document 2 describes a method for isomerizing trans-carotenoids into cis-isomers by heat treatment (particularly under subcritical conditions).
  • Non-Patent Document 1 describes the stability (depletion and change in isomer ratio) of krill-derived astaxanthin during processing steps including microwave drying.
  • Patent Document 1 is a method for cis-isomerizing lycopene using microwaves, and there are no examples of astaxanthin, so the effect of isomerization on trans-astaxanthin and the like is unclear.
  • the cis-isomer ratio by this method is high at about 67%, it is easily assumed that decomposition occurs at the same time due to the high treatment intensity.
  • the yield of cis-isomer is not shown, and its efficiency is unknown.
  • Patent Document 2 is a method for isomerizing carotenoids under subcritical conditions, and the effect of microwave treatment is not clear.
  • Non-Patent Document 1 krill (plankton containing astaxanthin) is dried using microwaves to obtain powder containing astaxanthin.
  • the microwave output is increased, the yield of cis-astaxanthin is low because the decomposition rate increases to a maximum of approximately 80%, while the yield of cis-astaxanthin is low.
  • the inventors have completed the present invention by subjecting a mixture of a raw material containing a carotenoid and an additive containing an emulsifier and fats and oils to microwave treatment.
  • the present invention is as follows.
  • a method for isomerizing trans-carotenoids to cis-carotenoids comprising the step of subjecting a mixture of a raw material containing trans-carotenoids and additives including fats and oils and an emulsifier to microwave treatment.
  • the content of the additive is 0.1% by mass or more and 50% by mass or less with respect to the total amount of the mixture.
  • the microwave output is 300 W or more.
  • trans-carotenoid is at least one selected from trans-adonirubin, trans-adonixanthin, trans-astaxanthin, trans-zeaxanthin and trans- ⁇ -cryptoxanthin.
  • trans-carotenoid is derived from bacteria, yeast, algae, animals or plants.
  • bacterium belongs to the genus Paracoccus.
  • a method for producing cis-carotenoids comprising the steps of: subjecting a mixture of a raw material containing trans-carotenoids and additives containing fats and oils and an emulsifier to microwave treatment; and recovering the isomerized cis-carotenoids after the microwave treatment step.
  • the amount of the additive added is 0.1% by mass or more and 50% by mass or less with respect to the total mixture.
  • the microwave output is 300 W or more.
  • trans-carotenoid is at least one selected from trans-adonirubin, trans-adonixanthin, trans-astaxanthin, trans-zeaxanthin and trans- ⁇ -cryptoxanthin.
  • trans-carotenoid is derived from bacteria, yeast, algae, animals or plants.
  • bacterium belongs to the genus Paracoccus.
  • the present invention makes it possible to isomerize trans-carotenoids to cis-carotenoids stably and in high yields.
  • FIG. 1 shows the cis-form ratio, concentration and residual rate of astaxanthin.
  • the present invention relates to a method for isomerizing a trans-carotenoid into a cis-carotenoid, the method comprising a step of subjecting a mixture of a raw material containing a trans-carotenoid and an additive containing an oil or fat and an emulsifier to microwave treatment.
  • the present invention also relates to a method for producing a cis-carotenoid, the method comprising a step of recovering the isomerized cis-carotenoid.
  • trans-carotenoids to be cis-converted examples include trans-astaxanthin, canthaxanthin, adonirubin, adonixanthin, ⁇ -carotene, ⁇ -cryptoxanthin, zeaxanthin, lutein, echinenone, 3-hydroxyechinenone, asteroidenone, ⁇ -apo-8'-carotenal, lactucaxanthin, tunaxanthin, capsanthin, capsorubin, violaxanthin, neoxanthin, fucoxanthin, siphonaxanthin, antheraxanthin, citranaxanthin, fucoxanthinol, amarousiaxanthin A, halocynthiaxanthin, diatoxanthin, peridinin, spirilloxanthin, rubixanthin, rhodoxanthin, alloxanthin, and the like, which
  • astaxanthin adonirubin, adonixanthin, canthaxanthin, ⁇ -carotene, ⁇ -cryptoxanthin, zeaxanthin, lutein, echinenone, 3-hydroxyechinenone, asteroidenone, and the like are preferably used, and these can be used alone or in appropriate combination.
  • carotenoids the structure of astaxanthin is shown below.
  • (A) is the trans structure of astaxanthin
  • (B) and (C) are the cis structures of astaxanthin (B: (9Z)-astaxanthin, C: (13Z)-astaxanthin).
  • the present invention has made it possible to efficiently isomerize trans-carotenoids to the cis structure under mild conditions, and has succeeded in improving the yield of the cis structure.
  • the raw material containing trans-carotenoid is not particularly limited, and any raw material can be used.
  • raw materials derived from bacteria, yeast, algae, animals, or plants can be mentioned (see below).
  • the trans-carotenoid may be a chemically synthesized product (e.g., a commercially available product).
  • Bacteria bacteria belonging to the genus Paracoccus, Agrobacterium, Brevibacterium, Brevundimonas, or Erythrobacter, and the like.
  • Yeast yeasts belonging to the genus Phaffia, Yarrowia, Rhodosporidium, Sporidiobolus, or Xanthophyllomyces, and the like.
  • Algae Haematococcus genus, Ulva genus, Chlorella genus, Dunaliella genus, Aurantiochytrium genus, Pinguiochrysis genus, Ochromonas genus, Phaeodactylum genus, Pleurochrysis genus, Chaetoceros genus, Algae belonging to the genera Chaetoceros, Pavlova, Cladosiphon, Sargassum, Undaria, Chlamydomonas, Spirulina, Arthrospira, Codium, Euglena, and Symbiodinium, etc.
  • Animals shrimp, crab, salmon roe, krill, eggs, etc.
  • Plants green and yellow vegetables (pumpkin, carrot, angelica tree, komatsuna, shiso, spinach, corn, paprika, etc.), fruits (mango, papaya, persimmon, apricot, citrus fruits, wolfberry, rose hips, etc.), flowers (marigold, adonis, etc.), etc.
  • Solvents used when extracting carotenoids from the above-mentioned raw materials include, for example, lower alcohols, ketone solvents, hydrocarbon solvents, and ether solvents.
  • lower alcohols ethanol, methanol, and isopropanol are preferably used, with ethanol being particularly preferred.
  • ketone solvents acetone and ethyl acetate are preferably used.
  • hydrocarbon solvents n-hexane and cyclohexane are preferably used.
  • ether solvents for example, tetrahydrofuran (THF) is preferably used. Supercritical carbon dioxide and the like can also be used.
  • wet bacterial cells obtained by subjecting the culture solution to a commonly known filtration method such as centrifugation can be used.
  • This wet bacterial cell can also be dried by a commonly known drying method such as spray drying, fluidized bed drying, rotary drum drying, or freeze drying to obtain dried bacterial cells that can be used as a raw material.
  • a bacterium in which the base sequence of DNA corresponding to 16S ribosomal RNA is substantially homologous to the base sequence set forth in SEQ ID NO: 1 is preferably used.
  • substantially homologous means that the sequence has, for example, 94% or more, 96% or more, or 98% or more homology, taking into consideration the error frequency in determining the base sequence of DNA.
  • the E-396 strain (FERM BP-4283) is particularly preferred.
  • a high carotenoid producing strain selected by mutating the E-396 strain to improve carotenoid productivity can also be used.
  • the E-396 strain has been internationally deposited with the International Patent Organism Depositary (IPOD) of the National Institute of Technology and Evaluation (NITE) (Room 120, 2-5-8 Kazusa Kamatari, Kisarazu City, Chiba Prefecture, 292-0818) as the international depositary authority as follows: Identification: E-396, Accession number: FERM BP-4283, Original deposit date: April 27, 1993
  • fats and oils are considered to be particularly effective in promoting isomerization, and emulsifiers are considered to be effective in improving stability. Therefore, fats and oils and emulsifiers can be used as additives in the present invention.
  • Fats and oils are a type of lipid, and basically refer to ester compounds of fatty acids and glycerin, but may also be fat-soluble nutrients. These ester compounds and fat-soluble nutrients are collectively referred to as "fats and oils" in this specification.
  • the origin of the fats and oils may be animal oil or vegetable oil.
  • the number of carbon atoms of the fatty acids constituting the fats and oils used in the present invention is not particularly limited.
  • the fats and oils may be short-chain fatty acids (having less than 6 carbon atoms (C)), medium-chain fatty acids (having 6-12 carbon atoms), long-chain fatty acids (having 13-21 carbon atoms), or very-long-chain fatty acids (having 22 or more carbon atoms), and the number of double bonds is not limited.
  • fatty acids having 8 to 24 carbon atoms are generally used.
  • carotenoids are reacted, fats and oils or fat-soluble nutrients used for food are preferred.
  • Fatty acids with 10 or more carbon atoms are also called higher fatty acids.
  • higher fatty acids include lauric acid (which has 12 carbon atoms (written as "C12"; the same applies to other fatty acids)), myristic acid (C14), palmitic acid (C16), stearic acid (C18), oleic acid (C18), linoleic acid (C18), linolenic acid (C18), arachidonic acid (C20), eicosapentaenoic acid (C20), and docosahexaenoic acid (C22).
  • lauric acid which has 12 carbon atoms (written as "C12"; the same applies to other fatty acids)
  • myristic acid C14
  • palmitic acid C16
  • stearic acid C18
  • oleic acid C18
  • linoleic acid C18
  • linolenic acid C18
  • arachidonic acid C20
  • fats and oils examples include the following. Olive oil, perilla oil, flaxseed oil, green nut oil, hemp seed oil, grape seed oil, soybean oil, corn oil, sesame oil, roasted sesame oil, mustard oil, rapeseed oil, argan oil, rice bran oil, peanut oil, safflower oil, macadamia oil, sunflower oil, palm oil, coconut oil, beef tallow, pork lard, etc.
  • fat-soluble nutrients include fat-soluble vitamins such as vitamin A, vitamin D, vitamin E, and vitamin K.
  • the emulsifier may be, for example, a surfactant.
  • the surfactant may be any of an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, and a cationic surfactant. Examples of these surfactants are shown below.
  • Nonionic surfactants Fatty acid-based (non-ionic): sucrose fatty acid ester, sorbitan fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester (polysorbate 20 (Tween 20), polysorbate 80 (Tween 80), etc.), fatty acid alkanolamide, polyglycerin fatty acid ester, glycerin fatty acid ester, propylene glycol fatty acid ester
  • Alkylphenol-based polyoxyethylene alkyl phenyl ether Others: sodium caseinate, lecithin, lysolecithin, saponin, etc.
  • ⁇ Cationic surfactants Quaternary ammonium salts: alkyltrimethylammonium salts, dialkyldimethylammonium salts Any of the above surfactants can be used, but particularly preferred are surfactants used for food.
  • excipients examples include dextrin, maltodextrin, starch, trehalose, cellulose, lactose, etc.
  • Antioxidants vitamin E (tocopherol), vitamin C, rosemary extract, etc.
  • Flavorings butter flavor, lemon flavor, etc.
  • the mixing ratio of the additive is 0.1% by mass or more and 50% by mass or less with respect to the entire mixture of the raw materials and the additives.
  • it is 1% by mass or more and 50% by mass or less with respect to the entire mixture, in another embodiment it is 1% by mass or more and 30% by mass or less, and in yet another embodiment it is 5% by mass or more and 30% by mass or less.
  • the microwave generating device is not particularly limited, and may be a microwave heater/dryer (either batch type or continuous type), a microwave experimental device, etc. Alternatively, a general household microwave oven, etc. may be used.
  • Microwaves are electromagnetic waves with a frequency of 300 MHz to 300 GHz, and preferably have a frequency in the range of 900 MHz to 10 GHz (eg, 2.45 GHz).
  • the microwave energy has an output of at least 300 W, for example, an output of 300 W or more. In one embodiment of the present invention, the output is appropriately selected from the range of 300 to 1500 W.
  • the microwave treatment time is 1 to 10 minutes, for example 3 to 5 minutes, and the energy applied in this case is 18 to 900 kJ, for example 90 to 300 kJ.
  • a raw material containing trans-carotenoids is mixed with additives including fats and oils and an emulsifier, and the mixture is subjected to microwave treatment to isomerize the trans-carotenoids to the cis-carotenoids, thereby obtaining carotenoids containing cis-carotenoids or a mixture of cis- and trans-carotenoids.
  • Microwave treatment promotes isomerization from trans to cis carotenoids.
  • Carotenoids can be dried at the same time by microwave treatment. Therefore, cis carotenoids can be recovered by recovering the dried product after microwave treatment as is.
  • the dried product can also be further treated by general methods applied to carotenoids, such as chromatography, concentration, crystallization, filtration, drying, etc.
  • the cis-isomerization ratio (also referred to as the cis-form ratio) can be improved to at least 1.1 to 8.2 times compared to the case in which no oils or fats and no emulsifier are added.
  • the ratio can be improved by 1.1 times or more, 1.2 times or more, 1.3 times or more, 1.4 times or more, 1.5 times or more, or 1.6 times or more.
  • the cis-isomerization ratio is calculated by the following formula.
  • Example 1 According to the method described in JP 2012-158569 A, the Paracoccus sp. E-396 strain was cultured and centrifuged to obtain a concentrated liquid containing carotenoids and bacterial cells. A concentrated culture solution of Paracoccus bacteria adjusted to an astaxanthin concentration of 2.5 g/L was mixed with powdered oil (5-30 wt%), and then the mixture was subjected to a microwave irradiation device ( ⁇ Reactor Ex) and dried in microwaves (output: 500 W or 1000 W, time: 3 or 5 minutes).
  • ⁇ Reactor Ex microwave irradiation device
  • the dried powder after the treatment was analyzed by HPLC, and the isomerization ratios and residual ratios of astaxanthin, adonirubin, and adonixanthin were calculated.
  • the HPLC analysis was performed using a mixed solvent of hexane/ethyl acetate/acetone (70:20:10, v/v/v) as the mobile phase and two connected columns (Luna 5 ⁇ m Silica (2)) at a column temperature of 40°C.
  • the cis-form ratio of astaxanthin, the astaxanthin concentration, and the residual rate of astaxanthin were measured when the oil or fat and the emulsifier were used alone.
  • the results are shown in Figure 1. From Figure 1, it is considered that fats and oils are mainly effective in promoting isomerization, and that emulsifiers are effective in improving stability.
  • the cis-form ratio, concentration, and residual rate of astaxanthin, adonirubin, and adonixanthin were measured when a combination (mixture) of fats and oils and an emulsifier was used.
  • the yield was calculated by multiplying the cis-carotenoid ratio (cis-ratio) by the residual carotenoid ratio.
  • cis-ratio cis-carotenoid ratio
  • Magic Fat 200 is a powdered oil made from palm oil
  • Emix AL is an emulsified powdered preparation made from tocopherol (a type of vitamin E)
  • Magical Ace N is a powdered oil made from rapeseed oil.
  • a higher cis-isomerization ratio was achieved when fats and oils were used compared to when they were not used.
  • a high cis-isomerization ratio was achieved without the need for a carotenoid isolation step such as cell disruption.
  • n represents a, c, g or t (position: 1350).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)

Abstract

Ce procédé d'isomérisation d'un trans-caroténoïde en cis-caroténoïde comprend une étape consistant à effectuer un traitement par micro-ondes sur un mélange de : une matière première qui contient un trans-caroténoïde ; et un additif qui contient des huiles et des graisses et un émulsifiant.
PCT/JP2024/002069 2023-06-12 2024-01-24 Procédé d'isomérisation de caroténoïde Pending WO2024257383A1 (fr)

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JP2023-096481 2023-06-12

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007522166A (ja) * 2004-02-10 2007-08-09 ネステク ソシエテ アノニム カロテノイド化合物のシス異性体を含む組成物及び方法
JP2019147742A (ja) * 2018-02-26 2019-09-05 カゴメ株式会社 シス‐リコピン含有組成物の製造方法、リコピンの異性化促進方法及びリコピン異性化用の触媒
US20210214291A1 (en) * 2020-01-10 2021-07-15 Michael Lloyd Rapid Thermal Isomerization of Lycopene

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007522166A (ja) * 2004-02-10 2007-08-09 ネステク ソシエテ アノニム カロテノイド化合物のシス異性体を含む組成物及び方法
JP2019147742A (ja) * 2018-02-26 2019-09-05 カゴメ株式会社 シス‐リコピン含有組成物の製造方法、リコピンの異性化促進方法及びリコピン異性化用の触媒
US20210214291A1 (en) * 2020-01-10 2021-07-15 Michael Lloyd Rapid Thermal Isomerization of Lycopene

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
YANG, S. ET AL.: "Effect of Thermal Processing on Astaxanthin and Astaxanthin Esters in Pacific White Shrimp Litopenaeus vanname i", JOURNAL OF OLEO SCIENCE, vol. 64, no. 3, 2015, pages 243 - 253, XP055274605, DOI: 10.5650/jos.ess14219 *
ZHAO, L. ET AL.: "Different effects of microwave and ultrasound on the stability of (all-E)- astaxanthin", JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY, vol. 54, no. 21, 2006, pages 8346 - 8351, XP002554065, DOI: 10.1021/jf061876d *

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