JP2007261983A - Deoxyglucosone formation inhibitor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a deoxyglucosone formation inhibitor excellent in safety. <P>SOLUTION: The deoxyglucosone formation inhibitor comprises, as an effective component, dimethylmonosulfide, dimethyldisulfide or dimethyltrisulfide, which is a sulfide compound contained in allium species plants. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a deoxyglucoson production inhibitor and a deoxyglucoson production inhibition method using the same. More specifically, the present invention relates to a highly safe deoxyglucoson production inhibitor and a deoxyglucoson production inhibition method using a compound contained in an experienced plant. Moreover, this invention relates to the foodstuff processed using the said deoxyglucosone production | generation inhibitor.

  Deoxyglucosone is a substance involved in browning reaction of food and saccharification reaction (glycation) in vivo. These browning reactions and saccharification reactions are dehydration condensation occurring between protein amino acids and sugar carbonyl groups, and are also referred to as amino-carbonyl reactions.

  Deoxyglucosone is usually contained in soy sauce, miso and sake at a ratio of about 45 to 73 ppm (Non-patent Document 1), and is also contained in foods such as honey, fruit juice and confectionery. When a large amount of deoxyglucosone is contained in the food, it causes a change in food such as a change in color (browning or fading) or a deterioration in flavor or taste.

  In addition, it is known that deoxyglucosone such as 1-deoxyglucosone and 3-deoxyglucosone is produced as an intermediate in the process of producing acrylamide, which has been a problem in processed potato products in recent years. In order to prevent the production, it is considered important to suppress the production of deoxyglucosone (see Non-Patent Documents 2 to 3, etc.).

  In addition, deoxyglucosone is absorbed in the body in the same way as glucose. Therefore, when a food containing a large amount of deoxyglucosone is ingested, the deoxyglucosone in the blood increases and binds to the protein in the blood to improve the physical condition. May be affected. Specifically, deoxyglucosone is an intracellular protein (hemoglobin, lens protein, etc.) or extracellular protein (albumin, immunoglobulin, collagen, various enzymes, etc.) via a lysine residue or arginine residue in vivo. This causes chronic diseases such as diabetes, neurological abnormalities (Non-patent Document 4), nephropathy (Non-patent Document 5), diseases derived from blood vessels (Non-patent Document 6), Alzheimer's disease (non-patent document 4). There are reports that it is a cause of aging (patent document 7), cataract (non-patent document 8), or aging.

  In the process of developing diabetic complications and arteriosclerosis from diabetes, it is clear that 3-deoxyglucosone is formed from glucose contained in blood at a high concentration via 2,3-enol substances. Therefore, it is considered that suppression of the production of deoxyglucosone is effective in preventing the onset of such diseases (Non-Patent Documents 10, 11, etc.).

Aminoguanidine and pyridoxamine are conventionally known as substances that suppress the production of deoxyglucosone (for example, Non-Patent Document 12). Aminoguanidine inhibits the process of deoxyglucosone reacting with proteins, and pyridoxamine inhibits the process of deoxyglucosone formation from Amadori transfer products, thereby suppressing the amino-carbonyl reaction in vivo. However, it is used as a therapeutic agent for various diseases such as diabetes, but it is limited to use in medical applications and cannot be used in the food field.
Edited by Satoshi Yoshizawa, “Science of Sake”, p67, Asakura Shoten (1995) Edited by Yoshito Sakurai, “General Food Dictionary (Fourth Edition)”, pp.156-158, Dobunshoin (1980) Yoshio Heno, Keiaki Kurihara, Mitsuru Uchiyama, “Food Hygiene”, pp.175-180, Asakura Shoten (1979) Miyata, T., et al, J. Clin. Invest, 92, 1242-1252 (1993) McCance, DR, et al, J. Clin. Invest, 91, 2470-2478 (1993) Vlasara, H., et al., Proc. Natl. Acad. Sci. USA, 89.12043-12047 (1992) Horiuchi, S., Trends Cardivasc. Med., 6, 163-168 (1996) Vitek, MP, et al., Proc. Natl. Acad. Sci. USA 91.4766-4770 (1994) Lyons, TJ, et al., Diabtes, 40, 1010-1015 (1991) Thornalley, PJ, Langborg, A., and Minhas, HS, Biochem.J., 344, 106-116 (1999) Hitomi Tsuji, Satoshi Miyata, Specific measurement method of saccharification reaction intermediate 3-deoxyglucosone, Dojin News, NO.98, 1-3, (2001) Williams, ME, Current Diabets Reports, 4; 441-446 (2004)

  An object of the present invention is to provide an agent (deoxyglucoson production inhibitor) that is effectively used to suppress the production of deoxyglucosone in food, and a method for inhibiting the production of deoxyglucoson in food. And In addition, when applying a deoxyglucosone production | generation inhibitor to a foodstuff, it is necessary to confirm the safety | security of the product itself produced by processing safety, such as itself, and heating. Therefore, a more preferred object of the present invention is to provide a deoxyglucosone production inhibitor containing as an active ingredient a component derived from a plant with dietary experience.

  Furthermore, the objective of this invention is providing the foodstuff by which the production | generation of deoxyglucoson is suppressed by processing with the said deoxyglucoson production inhibitor.

  The inventors of the present invention have focused on the functionality of plant extracts, and have intensively studied plant extracts that suppress the production of deoxyglucosone in foods. As a result, it was found that sulfide compounds contained in leeks, particularly dimethyl monosulfide, dimethyl disulfide and dimethyl trisulfide, exert an excellent inhibitory effect on the production of deoxyglucosone in the food. . The present invention has been completed based on such findings.

That is, the present invention includes the following modes.
(1) Deoxyglucosone production inhibitor Item 1. A deoxyglucosone production inhibitor containing a sulfide compound as an active ingredient.
Item 2. Item 2. The deoxyglucosone production inhibitor according to Item 1, wherein the sulfide compound has at least one functional group selected from a methyl group, a propyl group, an allyl group, and an isopropyl group.
Item 3. Item 3. The deoxyglucoson production inhibitor according to Item 1 or 2, wherein the sulfide compound is at least one compound selected from monosulfide, disulfide, and trisulfide.
Item 4. The sulfide compounds are dimethyl monosulfide, dimethyl disulfide, dimethyl trisulfide, allylpropyl monosulfide, allylpropyl disulfide, allylpropyl trisulfide, diallyl monosulfide, diallyl trisulfide, diallyl polysulfide, allylmethyl monosulfide, allylmethyl disulfide, allyl. At least one compound selected from methyl trisulfide, dipropyl monosulfide, dipropyl disulfide, dipropyl trisulfide, methylpropyl monosulfide, methylpropyl disulfide, methylpropyl trisulfide, diisopropyl monosulfide and dimethyltetrasulfide, Item 4. The deoxyglucosone production inhibitor according to any one of Items 1 to 3.
Item 5. Item 5. The deoxyglucosone production inhibitor according to any one of Items 1 to 4, which comprises a sulfide compound-containing fraction of a leek plant as an active ingredient.
Item 6. Item 7. The deoxyglucosone production inhibitor according to Item 6, wherein the sulfide compound-containing fraction is an extract of a leek plant.

(2) Deoxyglucosone production inhibiting method, one obtained by the method 7. Item 7. A method for inhibiting deoxyglucosone production in a test substance, comprising a step of treating the test substance with the deoxyglucosone production inhibitor according to any one of Items 1 to 6.
Item 8. The foodstuff by which the production | generation of deoxyglucosone processed using the deoxyglucosone production inhibitor in any one of claim | item 1 thru | or 6 is suppressed.

  According to the present invention, the production of deoxyglucosone in food can be suppressed, and as a result, the quality of food caused by the production of deoxyglucosone (specifically, coloring and discoloration, flavor and taste Deterioration) can be prevented. Moreover, according to the present invention, it is also possible to prevent the production of acrylamide in food by suppressing the production of deoxyglucosone in the food. Furthermore, according to the present invention, a large amount of deoxyglucosone can be prevented by inhibiting the production of deoxyglucosone in food, and by inhibiting the production of deoxyglucosone in vivo, It is thought that the bad influence (for example, refer nonpatent literature 4-9 etc.) by the deoxyglucosone in the living body can be prevented.

  The deoxyglucosone production inhibitor of the present invention comprises a sulfide compound contained in leeks, whose safety has been confirmed based on dietary experience, as an active ingredient. Therefore, it is highly safe and can be suitably used as an active ingredient used for the human body such as foods and pharmaceuticals.

  The deoxyglucosone production inhibitor of the present invention comprises a sulfide compound as an active ingredient.

  Here, deoxyglucosone targeted by the present invention includes 1-deoxyglucoson, 2-deoxyglucoson and 3-deoxyglucoson. The production inhibitor of the present invention only needs to have a production inhibitory action on at least one of these deoxyglucosons, and preferably at least 3-deoxyglucoson among these deoxyglucosons. Have a production-inhibiting action.

  In the sulfide compound which is an active ingredient of the present invention, the number of sulfur may be any number such as 1, 2, 3 and the position of sulfur located in the compound may be arbitrary. Furthermore, it may be modified with any functional group. For example, such a modified sulfide compound has 1 or 2 linear or branched chain alkyl having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. A sulfide compound modified with a group is included.

  Typical examples of the chain alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, isobutyl group, pentyl group, hexyl group, isohexyl group, pebutyl group, and methylpropyl group. 4,4-dimethylpentyl group, octyl group, 2,4,4-trimethylpentyl group, nonyl group, decyl group, undecyl group, and these branched chain isomer groups and similar groups. . Preferably, it is a C1-C4 lower alkyl group, More preferably, they are a methyl group, a propyl group, and isopropyl.

  Specific examples of the sulfide compound modified with a chain alkyl group include monosulfide, disulfide, and trisulfide such as dimethyl sulfide, dipropyl sulfide, isopropyl sulfide, and methylpropyl sulfide. Specifically, dimethyl sulfide such as dimethyl monosulfide, dimethyl disulfide and dimethyl trisulfide: dipropyl sulfide such as dipropyl monosulfide, dipropyl disulfide and dipropyl trisulfide: diisopropyl monosulfide: methylpropyl monosulfide, methylpropyl disulfide And methylpropyl sulfide, such as methylpropyl trisulfide: and dimethyltetrasulfide.

The sulfide compound used in the present invention includes a sulfide compound modified with one or two allyl groups (1-propenyl group). Such a sulfide compound may be modified with the alkyl group together with the allyl group.

Examples thereof include monosulfides, disulfides, and trisulfides such as diallyl sulfide, allyl propyl sulfide, and allyl methyl sulfide. Specifically, diallyl sulfides such as diallyl monosulfide, diallyl trisulfide and diallyl polysulfide: allylpropyl sulfides such as allylpropyl monosulfide, allylpropyl disulfide and allylpropyl trisulfide: allylmethyl monosulfide, allylmethyl disulfide and allylmethyl An example is allyl methyl sulfide such as trisulfide.

  The kind of the modified functional group of the sulfide compound used in the present invention is not limited to the specific group described above as long as the effect of the present invention is achieved, and is arbitrary. Moreover, the origin of the sulfide compound is not limited, and it may be a synthetic product or a natural product. A sulfide compound derived from a plant is preferable, and a sulfide compound derived from a leek plant is more preferable.

  Allium is a plant of the lily family, for example, onion, garlic (phosphorus stem), leek, raccoon, heron, scallion, leek (blue), leek (white), lily (rhizome), amadokororo, amana, enraiso, omoto , Katakuri, leek (leaves), leafy aloe (leaves), leafhopper (roots, rhizomes), oyster blanc, janohi, lily of the valley, bayflowers, red snapper, and dog saffron (seed). Among these, suitable plants include onions, leeks (white), raccoon, garlic, and the like, more preferably onions.

  It is reported that cruciferous plants such as cabbage, coffee, potato, tomato, passion fruit, grapes, pineapple, melon, green paste, watercress, etc. also contain sulfide compounds, and the content is low However, the present invention may use sulfide compounds derived from these plants (Perfumer & Flavorists, Vol. 18 May / June, 33-39, 1993).

  The deoxyglucosone production inhibitor of the present invention may contain a sulfide compound-containing fraction of the leek plant as an active ingredient. The sulfide compounds contained in the leeks include hydrogen sulfide, propylene sulfide, dimethyl sulfide, methylpropyl sulfide, methyl 1-propyl sulfide, allylmethyl sulfide, 1-propenylpropyl sulfide, diallyl sulfide and bis. Monosulfide, disulfide and trisulfide of (1-propyl) sulfide have been reported (issued by the Patent Office: Gazette of the Patent Office, Collection of Well-known and Conventional Techniques (fragrance) Part II Food Fragrance, pp856, 2000 (2000) ) .1.14 issued). The fraction containing the sulfide compound of the leek plant used in the present invention is preferably a fraction containing at least one sulfide compound selected from dimethyl monosulfide, dimethyl disulfide and dimethyl trisulfide in a high proportion or selectively. .

  Moreover, the essential oil of a leek plant can also be used as a sulfide compound containing fraction of a leek plant. For example, onion essential oils include di-2-propenyl sulfide, dimethyl disulfide, methyl-2-propenyl disulfide, dipropyl disulfide, propyl-2-propenyl disulfide, cis- and trans-1-propenylpropyl disulfide, di-2 -Propenyl disulfide, dimethyl trisulfide, dipropyl trisulfide, di-2-propenyl trisulfide, di-2-propenyl tetrasulfide, methanethiol, 2-hydroxypropanethiol, thiopropanal, 2-thiopropanal, 3-hydroxythio Propanal, thiocyanic acid, methylthiosulfinate, 3,4-dimethylthiophene and the like are known (Agnes Sass-Kiss et al, J. Sci. Food Agri. 1998, 76, 189-194; Sinha et al, J. Agric.F ood Chem. 1992, 40, 842-845; J. Agri. Food Chem. 1980, 28, 1037-1038; Boelens et al, J. Agr. Food Chem. 1971, 19, NO. 5, 984-991; Henk Maarse ed., Volatilecompounds in foods and beverages, 1991, Marrcel Dekker 203-271). In addition, the content of the essential oil contained in the onion is about 0.1%.

  The part of the leek used for obtaining the sulfide compound or the sulfide compound-containing fraction is not particularly limited, and may be the whole plant of the leek plant, or a partial part such as a leaf, stem, root, It may be either a flower or an apple stem (edible part). An edible part is preferred. For example, when an onion is used as an onion plant, leaves and stalks (edible part) can be used as suitable parts.

  The sulfide compound contained in the leek plant and the fraction containing the compound can be prepared and obtained by extracting a leek plant (for example, preferably an onion, leek, rakkyo) in the presence of a solvent. it can. Here, the leeks may be subjected to the extraction process as they are (raw) as they are, or may be subjected to the extraction process by slicing, slicing, squeezed or squeezed the liquid as it is. Good. Furthermore, the dried leek plant can be subjected to extraction treatment as it is or after being crushed and pulverized.

  As a solvent (extraction solvent) used for extraction, C1-C4 lower alcohols, such as methanol, ethanol, 1-butanol, 2-butanol, 1-propanol, and 2-propanol; Glycerin, propylene glycol, ethylene glycol And polyhydric alcohols such as butylene glycol; acetone, ethyl methyl ketone, ethyl acetate, methyl acetate, diethyl ether, cyclohexane, dichloromethane, edible deoxyglucosone, hexane, 1,1,1,2-tetrafluoroethane, 1, Mention may be made of organic solvents such as 1,2-trichloroethene or water. Preferred are lower alcohols such as ethanol and water.

  The extraction solvents listed above may be used singly or in combination of two or more. More preferably, it is a mixture of water and an organic solvent, and in particular, a mixture of lower alcohol and water (hydrous alcohol), more preferably a mixture of ethanol and water (hydrous ethanol). Specifically, a water-containing alcohol containing 40 to 60% by volume of water can be suitably used as the water-containing alcohol.

  Although it does not restrict | limit especially as a ratio of the said extraction solvent used with respect to the leek plant used for extraction, When converted into the weight ratio of the solvent used with respect to 100 weight part of raw leek plants, it is usually 50-20. Examples include 1,000 parts by weight, preferably 10 to 10,000 parts by weight.

  In addition, as a method for increasing the content ratio of the sulfide compound contained in the sulfide compound-containing fraction (or a method for selectively obtaining the sulfide compound), instead of or in addition to the above extraction method, compression, distillation (steam distillation, Preparation methods such as molecular distillation, fractional distillation, aroma distilate, recovery essence), extraction (tincture, maceration, percolation, oleoresin, concrete, absolute), subcritical or supercritical extraction methods can also be employed.

  The deoxyglucosone production inhibitor of the present invention may consist only of a sulfide compound-containing fraction obtained from the above-mentioned sulfide compound or leek plant, and is pharmaceutical or food as long as the effects of the present invention are not hindered. It may contain carriers and additives that are acceptable above. Carriers include water; lower alcohols such as ethanol; polyhydric alcohols such as propylene glycol and glycerin; sugars such as sugar, fructose, glucose, dextrin, cyclodextrin, and cyclic oligosaccharides; sugar alcohols such as sorbitol; Examples include gums such as chitosan and xanthan gum; distilled liquors such as sake, vodka and shochu; glycine and sodium acetate. Moreover, as an additive, emulsifiers, such as glycerol fatty acid ester and sucrose fatty acid ester, can be illustrated.

  Further, the deoxyglucosone production inhibitor of the present invention contains other components that are known to have a deoxyglucosone production inhibitory effect or that may be inhibited, as long as the effects of the present invention are not impaired. You can also. Such components include, for example, bayberry extract, enzyme-treated isoquercitrin, enzyme-treated rutin, quercetin, kaempferol, luteolin, myristic, flavonoids such as isoquercitrin, naringenin, and vitamin C, sodium erythorbate, vitamin E And vitamins.

  The form of the deoxyglucosone production inhibitor of the present invention is not particularly limited. For example, the deoxyglucosone production inhibitor of the present invention is used in the form of a solid such as a tablet, granule or powder, a liquid such as liquid, emulsion or suspension, or a semisolid such as a paste. it can.

  In addition, as a method for preparing the deoxyglucosone production inhibitor in a powder state, for example, a saccharide or sugar such as dextrin or cyclodextrin may be added to the sulfide compound-containing fraction obtained from the above-mentioned sulfide compound or leek plant as necessary. An excipient such as alcohol or a porous inorganic organic material such as calcium carbonate, ceramics, silica gel, activated carbon and the like can be added and prepared by a conventional method such as freeze drying, spray drying, or freeze grinding.

  Furthermore, examples of the method for preparing the deoxyglucosone production inhibitor in a liquid state include a method of blending an edible liquid into the sulfide compound-containing fraction obtained from the above sulfide compound or leek plant.

  In addition, content of the sulfide compound which is an active ingredient contained in a deoxyglucosone production | generation inhibitor can be suitably selected in the ratio of 1 to 100 weight% normally.

  The deoxyglucosone production inhibitor of the present invention can be suitably used for treatment of a composition containing a component that may produce deoxyglucosone. As a result, it is possible to suppress the deterioration caused by the production of deoxyglucosone (including discoloration and fading such as browning, flavor and taste deterioration) and the generation of acrylamide to maintain product quality and safety. It can be preferably used.

  Deoxyglucosone is known to be produced by an amino-carbonyl reaction between a protein or peptide amino acid and a sugar carbonyl group. Therefore, the composition targeted by the deoxyglucosone production inhibitor of the present invention includes foods (including supplements) containing amino acid components (amino acids, peptides or proteins) and sugars, pharmaceuticals, quasi drugs, cosmetics, There may be mentioned feed and feed.

  For example, foods can widely include foods and drinks that can produce deoxyglucosone by containing sugar and amino acid components (protein, peptide or amino acid).

  For example, soft drinks such as fruit juices, fruit drinks, functional drinks such as nutrition drinks and supplement drinks, cocoa, coffee drinks, roasted beverages, French fries, potato chips, french fries, corn snacks, sweet chestnuts, Sweets such as beans, waffles, carrots, rice crackers, crackers, cereals, wheat koji, almonds, pretzels, cookies, biscuits; croquettes, tonkatsu, fried chicken, french fries, dumplings, spring rolls, prepared foods, processed foods, sandwiches ; Curry food using stew, curry, curry powder, retort food such as risotto, pasta: burnt rice balls and rice with burnt eyes; food containing tempura such as pork, seafood, vegetables, noodles with food, udon, Nagasaki Champon Noodles, udon, cold noodles, buckwheat noodles, instant oil noodles, la Men, etc .; Stir-fried vegetables and rice (Chinese dumplings, fried rice, etc.); Foods, vegetables, foods and fruits baked in soy sauce (chicken, turkey); Vegetable tempura, fried fish Examples include various prepared dishes such as tempura of various ingredients and lunch boxes, alcohols such as Japanese sake, beer, fruit liquor, whiskey, amazake, or drinks that are warmed and consumed. In addition, the above is only an example, and it can be applied not only to these foods but also to other foods.

  A treatment method for suppressing the production of deoxyglucosone in each of these compositions (food, pharmaceuticals, quasi-drugs, cosmetics, feeds, feeds) and preventing alteration of the composition is described above. The method of making the deoxyglucosone production inhibitor of invention contact with each of these compositions can be mentioned. As a contact method, it selects suitably according to the form and manufacturing method of each composition, and it does not restrict | limit in particular. For example, taking food as an example, (1) a method of applying or spraying deoxyglucosone production inhibitor on the surface or cut surface of food, (2) a method of immersing food in a solution containing deoxyglucosone production inhibitor And (3) a method in which a deoxyglucosone production inhibitor is added to and mixed with food blends. In the case of the method (3), the addition time of the deoxyglucosone production inhibitor is not particularly limited, and it may be performed in the production or processing step of the food, or performed on the finally obtained food. May be. The deoxyglucosone production inhibitor is preferably used as a deoxyglucosone production inhibition method for drugs, quasi-drugs, cosmetics, feeds and feeds, as well as foods. be able to.

  The amount of deoxyglucosone production inhibitor added to the object varies depending on the type of the object to be treated (test object), the treatment method, etc., and cannot be specified unconditionally. For example, as a total amount of the sulfide compound contained in the final object, a ratio of 1 to 10,000 μg / g, preferably 1 to 100 μg / g can be exemplified.

  When the test object is immersed or sprayed, the total amount of sulfide compounds contained in the solution used for the immersion or spraying is 1 to 10,000 μg / g, preferably 10 to 1,000 μg / g. The ratio can be exemplified.

  Each composition thus treated (food, pigment, fragrance, pharmaceutical, quasi-drug, cosmetic, feed, etc.) suppresses the production of deoxyglucosone and, as a result, preferably produces the deoxyglucosone. No alteration (for example, including taste, flavor, discoloration, fading, malodor generation) can be prevented.

  Furthermore, since the production | generation of deoxyglucosone is suppressed, the production | generation of acrylamide which uses it as a production | generation intermediate | middle can be prevented.

  Accordingly, the present invention provides various compositions (food, dyes, fragrances, pharmaceuticals, quasi drugs, incense, and the like) that have been treated with the deoxyglucosone production inhibitor of the present invention to suppress the production of deoxyglucosone. Cosmetics, feed, etc.). The composition is treated with the deoxyglucosone deoxyglucosone production inhibitor of the present invention, and as a result, the production of deoxyglucosone is suppressed, and changes and alterations caused by deoxyglucosone (for example, The taste, flavor, discoloration, fading and generation of bad odor are not particularly limited as long as they are suppressed.

  Hereinafter, the contents of the present invention will be specifically described using the following experimental examples. However, the present invention is not limited to these. Unless otherwise specified, “%” means “% by weight” and “parts” means “parts by weight”. In the following experimental examples, various sulfide compounds (dimethyl monosulfide, dimethyl disulfide, dimethyl trisulfide) are manufactured by Oxford Chemicals, 3-deoxyglucosone and 2,3-diaminonaphthalene (DAN). Was obtained from Dojindo Co., Ltd., glucose (purity 99.9%) from ALFA Aesar, and asparagine (special grade) from Kida Chemical Co., Ltd.

Experimental Example 1 Suppression of 3-deoxyglucosone production by addition of sulfide compound When a mixture of glucose and asparagine is refluxed with methanol, acrylamide is produced from the Amadori transfer product in methanol via 3-deoxyglucosone production. (JR Pederson and JO Olsson, Analyst, 128,332-334 (2003); edited by Yoshito Sakurai, “General Food Dictionary (Fourth Revised Edition)”, Dobunshoin, pp.156-158 (1980); Masao, Kageihara Keiaki, Uchiyama Mitsuru, “Food Hygiene” Asakura Shoten, pp.175-180 (1979)).

  Therefore, in this experiment, as a composition capable of producing 3-deoxyglucosone, a methanol solution containing glucose and asparagine was used, and a sulfide compound was added to the solution to suppress the production of 3-deoxyglucosone. evaluated.

<Experiment method>
The production of 3-deoxyglucosone and the measurement thereof were carried out by our method (Hitomi Hitomi, Satoshi Miyata, “Specific measurement method of saccharification reaction intermediate 3-deoxyglucosone”, Dojin News, NO. 98, 1-3, (2001)). Specifically, 0.09 g of L-asparagine, 100 μL of 5 M aqueous sodium hydroxide solution, and 10 μL of various sulfide compounds (dimethyl monosulfide, dimethyl disulfide or dimethyl trisulfide) are added to a methanol solution of 10 mM glucose, The final volume was adjusted to 100 mL. About 10 mL of this solution is placed in a 20 mL vial, sealed with a butyl rubber stopper, and 0 to 2 hours (0 minutes, 15 minutes, 30 minutes, 60 minutes, 90 minutes) using a plate heater preheated to 60 ° C. 120 minutes).

  After cooling at room temperature, 100 μL of 0.1% 2,3-diaminonaphthalene (DAN) was added to 1 mL of the sample solution and allowed to react in a refrigerator at 5 ° C. for 16 hours. After the reaction, 4 mL of ethyl acetate was added to the reaction solution to extract the reaction product, evaporated to dryness, and then redissolved in 1 mL methanol was subjected to HPLC under the following conditions. As a control experiment, a solution to which no sulfide compound was added was treated in the same manner as described above (control group: blank).

  As a standard product, an adduct of 3-deoxyglucosone and DAN (1 mg / mL) was dissolved in methanol, and the peak of this adduct was confirmed as a peak of 3-deoxyglucosone. In addition, 0.1% DAN (100 μL) was added to 3-deoxyglucosone (1 mg / mL), held in a refrigerator at 5 ° C. for 16 hours, and used for analysis to confirm the reproducibility of the peak of the reaction product.

<HPLC conditions>
Column: ODS 80TM (250mm x 4.6mm, manufactured by Tosoh Corporation)
Column temperature: 30 ° C
Eluent:
Solution A: 5 mM phosphoric acid aqueous solution: acetonitrile: methanol = 70: 15: 15 (volume ratio)
Solution B: 5 mM phosphoric acid aqueous solution: acetonitrile: methanol = 40: 30: 30 (volume ratio)
Gradient condition: 100% solution A from 0 to 50 minutes, increase solution B from 50 minutes to 60 minutes Flow rate: 0.44 mL / min
Injection volume: 10μL
Detector: Fluorescence detector (JASCO)
Detection wavelength: 271 nm (excitation wavelength), 503 nm (fluorescence wavelength).

  The peak area corresponding to deoxyglucosone in each chromatogram was determined, and the amount of deoxyglucosone produced over time (μg / g) (reaction time 0, 15, 30, 60, 90, 120 minutes) was calculated.

  The results when dimethyl monosulfide is used as the sulfide compound are shown in Table 1, the results when dimethyl disulfide is used are shown in Table 2, and the results when dimethyl trisulfide is used are shown in Table 3, respectively.

  In the system in which no sulfide compound is added, 3-deoxyglucosone is produced by the reaction of glucose and asparagine and increases with the reaction time (control group), whereas dimethyl monosulfide, dimethyl disulfide or dimethyltrisulfide is increased. In the system to which sulfide was added, the production of 3-deoxyglucosone was suppressed, the production inhibitory effect was maintained regardless of the length of the reaction time, and partial decomposition seemed to occur.

  This mechanism is not limited, but since sulfide compounds undergo ene reaction and react nucleophilically, deoxyglucosone is produced from the amalide transfer product of sugar and amino acid through the process of sugar enolization. It is presumed that the production of deoxyglucosone is inhibited by the reaction of the sulfide compound in the process.

Experimental example 2
It is known that deoxyglucosone is produced as an intermediate in the process of producing acrylamide by the reaction of sugar and amino acid. For this reason, using the samples obtained in Experimental Example 1, the amount of acrylamide produced in these samples was determined, and it was investigated whether the inhibition of deoxyglucosone production had an effect on the production of acrylamide.

  The analysis method of acrylamide performed GC / MS analysis according to the well-known method, and calculated | required the value.

  Specifically, 5 mL of each sample solution obtained in Experimental Example 1 was transferred to a 50 mL brown stopper bottle, and after cooling, about 0.5 mL of concentrated sulfuric acid was added and stirred. About 10 g of potassium bromide was added thereto, and then 6 mL of 0.1 M potassium bromate was added. After bromination by standing in a refrigerator (4 ° C) for about 12 hours, 1 mol of sodium thiosulfate solution is added to each sample solution until the yellowish brown color of bromine disappears (about 2 mL) to decompose excess bromine. I let you. Next, the sample solution is transferred to a 100-mL separatory funnel and shaken with a separatory funnel for 5 minutes. The obtained aqueous layer was transferred to the original brown stopper bottle, and the ethyl acetate layer was transferred to a 100 mL Erlenmeyer flask. Add anhydrous sodium sulfate to the ethyl acetate layer and dehydrate. The filtrate was transferred to a 50 mL eggplant flask and the ethyl acetate layer was distilled off. To the obtained residue, 1 mL of hexane containing 20% acetone and 20 μL of triethylamine were added, dehydrobromated, and the monobromo derivative (monobromopropionamide) obtained by dehydrobromination was subjected to gas chromatography mass under the following conditions. Analysis was performed with an analyzer (GC-MS analyzer), and the amount of acrylamide produced was determined from the results of the calibration curve.

<Conditions for GC-MS analysis>
Equipment: GC 3800 (Varian), MS Saturn2100T (Varian)
Column: DB-5ms (Varian), 0.25mmi.d. × 30m
Injection volume: 1μL, splitless
Injection temperature: 250 ℃
Column temperature: 50 ° C (1 minute hold, 10 ° C / min) → 250 ° C (1 minute hold)
Transfer line temperature: 280 ℃
Carrier gas: Helium gas ion trap Temperature: 220 ° C
Ionization voltage: 70eV
Ionization mode: EI +.

  The results are shown in Table 4.

  As shown in Table 4, since the acrylamide concentration at the initial stage of the reaction was lowered by using the sulfide compound, it was found that the generation of acrylamide was suppressed by the sulfide compound. In addition, when the amount of production for each heating time is compared, the amount of acrylamide in the system to which dimethyl monosulfide, dimethyl disulfide and dimethyl trisulfide are added is larger than the amount of acrylamide in the control group (blank) after 60 minutes and 120 minutes. Generation was suppressed. This is thought to be due to the suppression of the production of oxyglucosone, which is an intermediate produced during the acrylamide production process.

  Table 4 also shows the results of a similar experiment using aminoguanidine (amount used 1 mM) and pyridoxamine (amount used 1 mM), which are known to suppress saccharification reactions in vivo.

  When both results are compared, it can be seen that the sulfide compound shows almost the same tendency as these aminoguanidine and pyridoxamine. From these, it was confirmed that the sulfide compound exerts an action of suppressing acrylamide formation in food and an action of suppressing sugar reaction in food due to the action of suppressing oxyglucosone production. .

Experimental example 3
(1) Preparation of onion supercritical CO ₂ extract 1600 g of raw onion was washed with water and then pulverized with a cutter, and filtered with a filter cloth to obtain about 400 g of a slightly pale yellow clear onion juice (onion pulverization) 1600 g of product). In this prepared onion juice, 190 mL (for 760 g of onion) was added and mixed with 60 mL of 95% by volume ethanol (hydrous ethanol) (onion: hydrous ethanol = 38: 3). 250 mL of the prepared onion-containing ethanol solution was filled in the extraction tank of the supercritical extraction system, and 700 L of carbon dioxide in a supercritical state adjusted to a pressure of 17.5 MPa and a temperature of 50 ° C. was introduced. After the introduction of carbon dioxide, the state is kept as it is for 25 minutes, and then the extraction tank is opened using a pressure regulating valve while adjusting the temperature, and carbon dioxide is released into the separation tank to produce 50 g of onion supercritical CO ₂ extract. Was collected from the sample collection port (onion for 760 g). The yield of the obtained supercritical CO ₂ extract (weight ratio of the extract to the weight of the raw onion used) was 6.6%.

(2) GC-MS analysis the onions were prepared by supercritical CO ₂ extract (sample 1) was subjected to GC / MS analysis of each following conditions.

<GC-MS analysis>
Equipment: GC 3800 (Varian), MS Saturn2100T (Varian)
Column: DB-5msitd (Micromass), 0.25mmi.d. × 30m
Injection volume: 1 μl, split (100: 1)
Injection temperature: 250 ℃
Column temperature: 50 ° C (1 minute hold, 10 ° C / min) → 250 ° C (1 minute hold)
Transfer line temperature: 280 ℃
Carrier gas: Helium gas Ion trap temperature: 220 ° C
Ionization voltage: 70eV
Ionization mode: EI +.

  The results are shown in Table 5. In addition, the identification of the substance was confirmed by subjecting the preparation of each sulfide compound to GC-MS analysis under the above-mentioned conditions and comparing it with the retention time.

As shown in Table 5, the onion supercritical CO ₂ extract contains many types of sulfide compounds, and it was confirmed that the sulfide compounds used in the present invention can be arbitrarily selected and used.

Experimental Example 4
Using the onion supercritical CO ₂ extract prepared in Experimental Example 3, the effect of suppressing the production of 3-deoxyglucosone was evaluated according to the method of Experimental Example 1. Specifically, 100 μL of the onion supercritical CO ₂ extract prepared in Experimental Example 3 was added to a methanol solution containing glucose and aspartic acid and reacted at 55 ° C. for 60 minutes to produce 3-deoxyglucosone. The amount was measured. Further, as a control, the amount of 3-deoxyglucosone produced was measured in the same manner for the system to which no supercritical CO ₂ extract was added (control group). The results are shown in Table 6.

As can be seen from the above results, the amount of 3-deoxyglucosone produced was suppressed by adding the supercritical CO ₂ extract compared to the case of no addition (control group). In particular, the supercritical CO ₂ extract held for 25 minutes under supercritical conditions is highly effective in suppressing the production of 3-deoxyglucosone and produces about 57% of 3-deoxyglucosone as compared to the control group without addition. Was lowered. This is considered to be due to an increase in the concentration of sulfide contained in the extract by keeping it under supercritical conditions for 25 minutes as compared to an extract obtained without keeping critical extraction in supercritical CO ₂ .

Experimental Example 5
For various sulfides (Table 7) having different numbers of functional groups and sulfides, including the sulfides shown in Experimental Example 3, the effect of suppressing the production of deoxyglucosone was evaluated according to Experimental Example 1. Specifically, 10 μL of each sulfide was added to a methanol solution containing glucose and aspartic acid and reacted at 55 ° C. for 60 minutes to measure the amount of 3-deoxyglucosone produced. In addition, as a control, the amount of 3-deoxyglucosone produced was measured in the same manner for the system to which no sulfides were added (control group). The results are shown in Table 7.

  As shown in Table 7 above, the addition of sulfides significantly suppressed the production of deoxyglucosone. Moreover, the difference in the functional group of sulfides did not recognize a big difference in the deoxyglucosone production inhibitory effect. However, the diallyl group tended to be more effective as the number of mono> tri> poly and sulfur decreased. The allylmethyl group also showed the same tendency. For other sulfides, there was almost no effect due to the number of sulfur.

Claims (8)

  A deoxyglucosone production inhibitor containing a sulfide compound as an active ingredient.   The deoxyglucosone production inhibitor according to claim 1, wherein the sulfide compound has at least one functional group selected from a methyl group, a propyl group, an allyl group, and an isopropyl group.   The deoxyglucosone production inhibitor according to claim 1 or 2, wherein the sulfide compound is at least one compound selected from monosulfide, disulfide and trisulfide.   The sulfide compounds are dimethyl monosulfide, dimethyl disulfide, dimethyl trisulfide, allylpropyl monosulfide, allylpropyl disulfide, allylpropyl trisulfide, diallyl monosulfide, diallyl trisulfide, diallyl polysulfide, allylmethyl monosulfide, allylmethyl disulfide, allyl. Is at least one compound selected from methyl trisulfide, dipropyl monosulfide, dipropyl disulfide, dipropyl trisulfide, methylpropyl monosulfide, methylpropyl disulfide, methylpropyl trisulfide, diisopropyl monosulfide and dimethyltetrasulfide, The deoxyglucosone production inhibitor according to any one of claims 1 to 3.   The deoxyglucosone production inhibitor according to any one of claims 1 to 4, which contains a sulfide compound-containing fraction of a leek plant as an active ingredient.   The deoxyglucosone production inhibitor according to claim 6, wherein the sulfide compound-containing fraction is an extract fraction of a leek plant.   A method for inhibiting the production of deoxyglucosone in a test substance, comprising a step of treating the test substance with the deoxyglucosone production inhibitor according to any one of claims 1 to 6. The foodstuff by which the production | generation of deoxyglucosone processed using the deoxyglucosone production inhibitor in any one of Claims 1 thru | or 6 was suppressed.