JP4168196B2 - Acrylamide production inhibitor - Google Patents

Description

  The present invention relates to an acrylamide production inhibitor capable of inhibiting the production of acrylamide generated in food cooking and processing steps. More specifically, the present invention provides an acrylamide production inhibitor capable of inhibiting the production of acrylamide by using an extract of an experienced plant extract or a compound contained therein as an active ingredient and using it in a food cooking / processing step. It relates to the agent.

  Furthermore, the present invention relates to a food treating agent using the acrylamide production inhibitor, an acrylamide production inhibition method, and a food product in which the production of acrylamide is inhibited.

  In recent years, it has been reported that a highly carcinogenic substance called acrylamide is produced by cooking food at high temperature such as fried bread such as French fries and rusk (Stockholm report) (Non-patent document 1). ~ 4).

  Acrylamide is not produced when the food is boiled, but it is known that a large amount of acrylamide is produced when the food is fried in oil or baked at high temperatures. So-called oil-boiled foods (such as fried potatoes, potato chips, biscuits, fried chicken, French fries, etc.) prepared by cooking these ingredients with oil are used in the form of processed foods and prepared dishes for business use or general consumers in the food service industry. Since it is often provided or used as an ingredient in side dishes and lunch boxes, the suppression of acrylamide production is an important issue that should be solved early.

  Under such circumstances, the cause of acrylamide formation is being understood. Specifically, it has been reported that acrylamide is generated due to the occurrence of an amino-carbonyl reaction in food with asparagine and glucose (Non-Patent Documents 5 to 6). In this way, it can be seen that potatoes, which are generally said to be easy to produce acrylamide, contain asparagine / aspartic acid, which is the cause of acrylamide formation, at a ratio of 0.82 g / 100 g, followed by glutamic acid.

  Amino-carbonyl reaction generally refers to the reaction of amino groups (derived from amino acids such as asparagine and methionine) and carbonyl groups (derived from reducing sugars) in compounds, and browning that occurs during cooking such as oil frying or frying. The phenomenon is also known to be caused by an amino carbonyl reaction.

  The browning of food caused by the amino-carbonyl reaction not only affects the flavor and color of food, but also reduces the commercial value of processed foods by browning the golden color preferred by consumers. Cause. For this reason, it is a problem to be solved. Although various uses of antioxidants have been proposed as a method for suppressing browning of food produced in such cooking (for example, Non-Patent Documents 7 and 8), the expected effect has not been obtained. is there.

  The use of the above-mentioned antioxidants can be considered as a method for suppressing acrylamide caused by the amino-carbonyl reaction as in the browning phenomenon. However, since the generation of acrylamide occurs particularly by cooking food at high temperature, the antioxidant itself is quickly oxidized during use (during cooking) and loses its effectiveness, which is not a very promising method.

Thus, although there is an urgent need for measures to suppress the production of acrylamide in foods, no component that can suppress the formation of acrylamide, particularly a component that can suppress the formation of acrylamide during oiling, has not been found. Is the actual situation.
Swedish National Food Agency website HYPERLINK "http://www.slv.se" http://www.slv.se Rosen, J. & Hellenas, KEThe Analyst 127 (2002) 880-882 WHO FAO / WHO Consultation on the Health Implications of Acrylamide in Foods (Geneva, 25- June 2002) IARC IARC Monographs on the Evaluation of Carcinogenic Risks to Humans 60, (1994) 389 DSMottram, BLWedzicha, ATDodson, Nature, No.419, 2002 448-449 rHStadler, I. Blank, N. Varga, F. Robert, J. Hau, PAGuy, MC. Robert, S. Riediker, Nature, No. 419, (2002) p. 449 Ota Shizuyuki: Food and Antioxidants (1987) Food Materials Research Group, 138 pages Ota Shizuyuki: Food and Antioxidants (1987), Food Materials Research Group, 127

  The objective of this invention is providing the formulation for suppressing the acrylamide production | generation in a foodstuff, and its method. In general, when a certain thing is applied to food, it is necessary that the safety of the product itself and the safety of the product generated by heating are confirmed. Moreover, it is preferable that the product itself does not have a taste, smell or color so as not to affect the original taste, flavor and color of the food.

  From this point of view, the present invention has an object to provide an acrylamide production inhibitor that is safe and does not adversely affect the food processed in terms of color and odor. Moreover, this invention is providing the acrylamide production | generation suppression method of the foodstuff using the said acrylamide production | generation inhibitor. Furthermore, the objective of this invention is providing the foodstuff by which the production | generation of acrylamide processed by the said method was suppressed.

  The inventors of the present invention have intensively researched to solve the above-mentioned problems. As a result, an extract prepared by extracting with a solvent such as a lower alcohol from a lily family or a cruciferous plant is used to produce acrylamide in food. And found that the active ingredient is a specific sulfide compound.

  The inventors of the present invention have confirmed that these sulfide compounds and plant extracts containing them can be effectively used for acrylamide production inhibition treatment with almost no adverse effects such as color and odor on foods to be treated.

The present invention has been completed based on such findings.
That is, the present invention is an acrylamide production inhibitor for foods listed in the following (1) to (7):
(1) A food acrylamide formation inhibitor containing a sulfide compound as an active ingredient.
(2) The acrylamide production inhibitor according to (1), wherein the sulfide compound is at least one selected from the group consisting of allyl methyl trisulfide, dimethyl tetrasulfide, and dimethyl disulfide.
(3) The acrylamide production inhibitor according to (1), wherein the sulfide compound is allylmethyl trisulfide.
(4) The acrylamide production inhibitor according to (1), which contains a sulfide compound-containing fraction of a lily family plant as an active ingredient.
(5) The acrylamide production inhibitor according to (4), wherein the sulfide compound-containing fraction is an essential oil fraction of a lily family plant or a Brassicaceae family.
(6) The sulfide compound-containing fraction is at least one selected from the group consisting of an allylmethyltrisulfide-containing fraction, a dimethyltetrasulfide-containing fraction, and a dimethyldisulfide-containing fraction (4) or (5) An acrylamide production inhibitor described in 1.
(7) Inhibition of acrylamide production according to (4) or (5), wherein the liliaceae plant is one or more selected from the group consisting of onion, leek, garlic, leek, raccoon, bamboo shoot, and leek Agent.

Moreover, this invention is a processing agent hung up to the following (8) used for processing of foodstuffs irrespective of the use purposes and uses, such as acrylamide production | generation suppression and quality maintenance.
(8) A food treating agent comprising the acrylamide production inhibitor according to any one of (1) to (7).

Furthermore, this invention relates to the acrylamide production | generation suppression method and foodstuff which are hung up over following (9)-(10):
(9) The acrylamide formation inhibitor according to any one of (1) to (7) or the food treating agent according to (8) is added to the oil at the time of oiling, or the food A method for suppressing acrylamide production in foods, comprising a step of adhering to a surface.
(10) A food in which the production of acrylamide is suppressed by being treated with the acrylamide production inhibitor according to any one of (1) to (7) or the food treating agent according to (8). .

  Note that “acrylamide generation” is a phenomenon of acrylamide formation that generally occurs when vegetables are heat-treated, such as oil frying or stir-fry, and the present invention aims to suppress acrylamide formation that occurs in foods during cooking. It is. As described above, acrylamide formation is generally explained to be caused by an amino-carbonyl reaction (Maillard reaction) between asparagine and glucose contained in vegetables such as potato. Is not to be done. For example, not only in the reaction of asparagine with glucose, but also in amino carbonyl reaction processes such as amino acids other than asparagine (for example, methionine, glutamine or cysteine) and sugars other than glucose (for example, fructose, galactose, lactose, sugar or butanedione) This also applies to the case where an intermediate substance) generates an acrylamide through an amino-carbonyl reaction.

  ADVANTAGE OF THE INVENTION According to this invention, the production | generation of the acrylamide which arises in a cooking, the processing of a foodstuff, etc. can be suppressed, the bad influence by ingesting acrylamide can be prevented by this, and a safe diet can be provided. In particular, the acrylamide production inhibitor of the present invention comprises a sulfide compound contained in a lily family plant such as an onion and the like whose safety has been confirmed based on food experience as an active ingredient. Therefore, it is highly safe and can be suitably used as a food treating agent.

  In addition, the acrylamide production inhibitor of the present invention has almost no problem with odor and coloring derived from liliaceae and cruciferous plants, and does not substantially impair the flavor of processed foods (oiled foods). Can be used effectively to maintain quality.

  The present invention will be described below.

  The acrylamide production inhibitor of the present invention is characterized by containing a sulfide compound as an active ingredient.

  The sulfide compound used in the present invention is a compound having a disulfide compound, a trisulfide compound or a tetrasulfide compound as a skeleton. Any of the skeletons of these sulfide compounds may be modified with any functional group.

  For example, a sulfide compound modified with a linear or branched chain alkyl group having 12 carbon atoms, preferably not exceeding 8 carbon atoms, is included. Here, typical chain alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, isobutyl group, pentyl group, hexyl group, isohexyl group, pebutyl group, 4,4. -A dimethyl benzyl group, an octyl group, a 2,4,4-trimethylpentyl group, a nonyl group, a decyl group, an undecyl group, these branched isomer groups, and the same group can be illustrated. Preferably it is a C1-C6 lower alkyl group, More preferably, it is a methyl group. More preferred examples of the sulfide compound modified with a chain alkyl group include dimethyl disulfide and dimethyl tetrasulfide.

  The sulfide compound used in the present invention also includes a sulfide compound modified with an allyl group (1-propenyl group). Such a sulfide compound may be modified with the above alkyl group together with an allyl group, and preferable examples thereof include allylmethyl trisulfide.

  Furthermore, the sulfide compound used in the present invention includes a sulfide compound modified with an aryl group. Here, examples of the aryl group include those having a monocyclic (eg, phenyl group) or bicyclic aromatic group (eg, naphthyl group) containing 6 to 10 carbon atoms in the ring portion. The monocyclic or bicyclic aromatic group may have a substituent, and examples thereof include a substituted phenyl group or a substituted naphthyl group having a lower alkyl group having 1 to 6 carbon atoms.

  The type of the modified functional group of the sulfide compound used in the present invention is not limited to the above and is arbitrary, and the type of the functional group is not particularly limited. Moreover, the origin of the sulfide compound used in the present invention is not limited, and it may be a synthetic product or a natural product. It is preferably derived from a natural product, more preferably derived from a plant such as a lily family or a cruciferous family, particularly an edible plant.

  The acrylamide production inhibitor of the present invention may contain a sulfide compound-containing fraction of a liliaceae plant or a cruciferous plant as an active ingredient. A lily family plant is preferred because of the high content of sulfide compounds. In the above sulfide compound-containing fraction, specific examples of the “sulfide compound” include the sulfide compounds described above, and dimethyl disulfide, dimethyl tetrasulfide, and allylmethyl trisulfide are preferred.

  Here, examples of the lily family include onion, garlic (preferably apple stalk), leek, raccoon, heron, leek, wakegi, lily (preferably rhizome), amadokoroko, amana, enraiso, omoto, katsuri, leek (preferably And leaves), yellow aloe vera (preferably leaves), leafhopper (preferably roots and rhizomes), oyster blanc, janohi, lily of the valley, bayflowers, red snapper, and dog saffron (preferably seeds). Preferred are onion, garlic, leek, raccoon, leek, wakegi, and leek, and more preferred is onion. Examples of the cruciferous plants include cabbage, rapeseed and radish. Preferred are cabbage and radish.

  It is reported that coffee, potato, tomato, passion fruit, grape, pineapple, melon, watercress and the like also contain sulfide compounds, and although the content is small, sulfide compounds derived from these plants Is not excluded (Perfumer & Flavorists, Vol. 18 May / June, 33-39, 1993).

  Examples of the lily family plant onions used in the present invention include a wide range of onions that are usually used for food. Specifically, a lily family plant onion (Allium cepa LINNE) can be illustrated. The part to be used is not particularly limited, and may be the whole plant of the liliaceae plant onion, or may be any of partial parts such as leaves, stems, roots, flowers, or stalks (edible part). Preferably it is an apple stem (edible part).

  There are many cultivated varieties of lily family onions, and different types are produced by selection and breeding. Lily family onion varieties can be broadly divided into two groups: sweet onions and spicy onions. Sweet onions are cultivated in Spain and Italy, but are rarely cultivated in Japan. On the other hand, spicy onions were introduced to Japan via the United States via Central Asia (Romania, Yugoslavia), and most of the cultivated in Japan are in this group. The onion used by this invention can use any onion regardless of the distinction of these sweet onions and spicy onions. Examples of the spicy onion include late-type onions such as yellow, brown bear, sekihoku, heavenly heart, moon cake, northern maple 86, maple, and super northern maple, and can also be preferably used in the present invention. it can. These onions are readily available from agricultural cooperatives, retailers such as supermarkets and shops.

  As described above, the acrylamide production inhibitor of the present invention selectively uses one or more sulfide compounds selected from allyl methyl trisulfide, dimethyl tetrasulfide, and dimethyl tetrasulfide as an active ingredient. It is characterized by.

  Originally, onions 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-hydroxythiopro It is known to contain scent components such as panal, thiocyanic acid, methylthiosulfinate, 3,4-dimethylthiophene (Agnes Sass-Kiss et al: J. Sci. Food Agri. 1998, 76, 189- 194, Sinha et al: J. Agric. Food 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). These ingredients are contained in essential oils in onions. In addition, the content of the essential oil contained in the onion is about 0.1%.

  Dimethyl tetrasulfide used in the present invention is a component contained in a lily family plant, and it is reported that it is produced at a high concentration by stress load, for example, when a leek or the like is cut (Japan Patent Office). , JPO Gazette, published on January 14, 2000, Collection of well-known and commonly used techniques (fragrance) Part II Food Fragrance). The onion contains allyl methyl trisulfide and dimethyl tetrasulfide, which are objects of the present invention.

  Similarly, it has been reported that garlic, a lily family plant, contains components such as alliin, cycloallyin, S-methylcysteine sulfoxide, γ-glutamyl-S-allyl-L-cysteine, and glutathione. And dimethyl disulfide, allyl methyl trisulfide and dimethyl tetrasulfide, which are objects of the present invention.

  Similarly, leek, a lily family plant, is known to contain allylmethyl trisulfide used in the present invention in addition to disulfide compounds such as methylpropyl disulfide and dipropyl disulfide. The allyl methyl trisulfide is a component contained in leek and garlic garlic, and is reported as a substance that inhibits platelet aggregation and inhibits tumor formation (Hiroyuki Nishimura, Toyohiko Ariga, foods with spice ingredients) Function (Iwai & Nakatani) Chapter 7 Active ingredients of Gyoja garlic and its physiological functions, 199-299, Mitsuseikan, May 1989, T. Ariga et al., Lancet, 150 (1981), VLSparnins et al. Carcinogenesis, 9, 131 (1988)).

  In addition, rakkyo contains dimethyl disulfide in a ratio of 87% in the sulfide compound, and asatsuki and leek also contain dimethyl disulfide, allyl methyl trisulfide and dimethyl tetrasulfide, which are objects of the present invention.

  Cabbage belonging to the Brassicaceae plant includes dimethyl sulfide, dibutyl sulfide, dimethyl disulfide, methyl ethyl sulfide, methyl propyl disulfide, dipropyl disulfide, propyl butyl disulfide, propyl-3-butenyl disulfide, di-3-butenyl. It is known to contain scent components such as disulfide, dimethyltrisulfide, methanethiol, methyl isothiocyanate, n-methylsulfinylpropyl isothiocyanate, 2-propenyl cyanide (Atake Naohiko: Food Industry 1994.7. No. 15, p62, edited by Masao Fujimaki, revised food chemistry, 1976, Asakura Shoten, p249-257).

  In addition, it is known that Brassicaceae plants contain allyl isothiocyanate and its precursor glucosinolate.

  The fractions of these Liliaceae or Brassicaceae plants that contain sulfide compounds (allylmethyltrisulfide, dimethyltetrasulfide, and dimethyldisulfide) are lilyaceae plants (for example, preferably onion, raccoon, leek, Leek, garlic, etc.) can be prepared and obtained by extraction treatment in the presence of a solvent. Here, the plant may be subjected to the extraction treatment as it is (raw), or may be subjected to the extraction treatment with raw sliced or shredded products, crushed material, or squeezed liquid. . Furthermore, the dried plant material can be subjected to extraction treatment as it is or after being crushed and pulverized. As an aspect of a suitable thing to use for an extraction process, the squeezed liquid obtained by pressing after crushing raw can be mentioned.

  Solvents used for extraction (extraction solvent) include C1-C4 lower alcohols such as methanol, ethanol, 1-butanol, 2-butanol, 1-propanol, and 2-propanol; glycerin, propylene glycol, and ethylene glycol And polyhydric alcohols such as butylene glycol; acetone, ethyl methyl ketone, ethyl acetate, methyl acetate, diethyl ether, cyclohexane, dichloromethane, edible fats and oils, hexane, 1,1,1,2-tetrafluoroethane, 1,1, Mention may be made of 2-trichloroethene and 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 other components, and particularly 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.

  The ratio of the extraction solvent used for the plant used for extraction is not particularly limited, but is usually 50 to 20,000 parts by weight, preferably 10 to 10,000 parts by weight, based on 100 parts by weight of the raw plant. It can be illustrated.

  In addition, as a method for increasing the concentration of allylmethyltrisulfide, dimethyltetrasulfide, or dimethyldisulfide in the extracted fraction, instead of or in combination with the above extraction method, compression, distillation (steam distillation, fractional distillation, aroma It is possible to employ methods such as a distilate, recovery essence), extraction (tincture, maceration, percolation, oleoresin, concrete, absolute), subcritical or supercritical extraction methods.

  The optimal extraction conditions are set by analyzing the amount of the target sulfide compound (dimethyldisulfide, allylmethyltrisulfide or dimethyltetrasulfide) contained in the extract obtained by the above method, for example, by HPLC or the like. Fine adjustments can be made. In addition, as a method for isolating and obtaining a target sulfide compound (dimethyl disulfide, allylmethyl trisulfide, and dimethyltetrasulfide) or a fraction containing it in a high concentration from the extract obtained by the above method, HPLC is used. Can be used. Although such HPLC conditions are not particularly limited, HPLC under the following conditions can be exemplified as an example.

HPLC: JASCO Gulliver980 Series Column: developers C ₃₀ -UG-5 (reverse phase column, Nomura Chemical Co., Ltd., 250 × 4.6mmi.d.)
Eluent: Acetonitrile: Water: HMF = 70: 27: 3
Injection volume: 10μl
Flow rate: 1ml / min
Detection wavelength: 211 nm (allyl methyl trisulfide, dimethyl disulfide), 240 nm (dimethyl tetrasulfide).

  The acrylamide production inhibitor of the present invention may consist only of the aforementioned sulfide compound or a sulfide compound-containing fraction of the liliaceae plant or cruciferous plant, and is acceptable for food hygiene as long as the effects of the present invention are not hindered. It may contain a carrier and an additive. 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; oils and fats, glycine and sodium acetate.

  Moreover, the acrylamide production | generation inhibitor of this invention can also contain another component as long as it does not impair the effect of this invention. Examples of other components include emulsifiers such as glycerin fatty acid esters and sucrose fatty acid esters, vitamin C, sodium erythorbate, vitamin E, bayberry extract, antioxidants such as enzyme-treated rutin, and salt. .

  The form of the acrylamide production inhibitor of the present invention is not particularly limited. For example, the acrylamide production inhibitor of the present invention can be used in any form such as a solid such as a tablet, granule or powder, a liquid such as liquid or emulsion, or a semi-solid such as paste. In addition, when using a fraction containing a sulfide compound such as a liliaceae or cruciferous plant as an active ingredient, it should be used in the form of a liquid preparation obtained by emulsifying the essential oil with an emulsifier, with the essential oil or oleoresin containing the sulfide compound. You can also.

  In addition, as a method for preparing the acrylamide production inhibitor in a powder state, for example, a saccharide or sugar such as dextrin or cyclodextrin, if necessary, in the sulfide compound-containing fraction such as the above-mentioned sulfide compound or liliaceae or cruciferous plant. Examples include a method of adding an excipient such as alcohol or a porous inorganic organic material such as calcium carbonate, ceramics, silica gel, activated carbon, and then performing lyophilization, spray drying, freeze pulverization, or the like. Moreover, as a method of preparing the acrylamide production inhibitor in a granular state, for example, ethanol is mixed with the sulfide compound or the sulfide compound-containing fraction to prepare an ethanol preparation (usually 10 to 60% by weight ethanol concentration), and then A method of granulating by adsorbing this to calcium carbonate can be mentioned.

  For example, the powdery or granular acrylamide production inhibitor thus prepared can be suitably used for a solid food material. In particular, powdered or granular materials can be added and blended with the target food material and mixed uniformly. Examples of such food materials include tempura and fried clothing components.

  Furthermore, as a method for preparing the acrylamide production inhibitor in a liquid state, for example, a method of blending edible liquid oil into a sulfide compound-containing fraction such as the above-mentioned sulfide compound or a lily family or a cruciferous plant can be exemplified. The liquid preparation thus prepared is not particularly limited, but can contain edible liquid oil in a proportion of 90 to 99% by weight.

  For example, the liquid acrylamide production inhibitor prepared in this way can be used by adding to the oil to be used. That is, by preparing the acrylamide production inhibitor in a liquid state using edible fats and oils, the acrylamide production inhibitor can be evenly mixed with the oil for oiling and can be brought into uniform contact with the surface of the oiling material. Moreover, it can be mentioned as an advantage that separation from the oil does not occur and the shape and the like of the oiled food can be easily processed. The acrylamide production inhibitor having the above liquid form can also be prepared by immersing an onion such as onion in rapeseed oil or the like, and transferring the sulfide compound targeted by the present application to the oil or fat (for example, liquid Oil preparations, flavor oils, etc.).

  In addition, content of the sulfide compound (allyl methyl trisulfide, dimethyl disulfide, dimethyl tetrasulfide) which is an active ingredient of the acrylamide production inhibitor can be appropriately selected from the range of usually 1 to 100% by weight in total.

  The acrylamide production inhibitor of the present invention can be suitably used for acrylamide production inhibition treatment of processed foods, acrylamide production inhibition treatment during the manufacturing process of processed foods, and processing steps for maintaining quality. In this sense, the acrylamide production inhibitor of the present invention can be defined as a food treating agent regardless of the purpose of use.

  The types of ingredients that can be used for the acrylamide production inhibitor of the present invention and the types of processed foods containing the same include vegetables such as Chinese cabbage, celery, Japanese radish, and Japanese cypress, mushrooms such as shiitake, and mushrooms. Kinds: Root vegetables such as burdock, potato, lotus root, sweet potato, carrot, long potato and yam; fruit vegetables such as eggplant, shishito, bell pepper, pepper, cucumber, tomato and soybean. Preferred are sweet potato, potato, corn, lotus root, mushroom and burdock. It can also be applied to fields handling foods such as seafood and livestock.

  Examples of the method for preventing acrylamide formation of the food include a method of bringing the aforementioned acrylamide production inhibitor (or food treatment agent) of the present invention into contact with the food before the heat treatment.

  The contact method is not particularly limited, but a method of applying or spraying an acrylamide formation inhibitor (or food treatment agent) on the surface or cut surface of food, or a food in a solution containing an acrylamide formation inhibitor (or food treatment agent). And a method of adding and mixing an acrylamide formation inhibitor (or food treatment agent) to food.

  In addition, regardless of the timing of addition and mixing of the acrylamide formation inhibitor (or food processing agent) to food (including those processed to a state where the original shape is not retained), for example, it may be performed during the heat treatment process of food. In addition, it may be performed on the finally obtained processed product. Specifically, it can be added to edible fats and oils used in oil cans, and the oils can be used for oily or frying treatments.

  The amount of the acrylamide production inhibitor (or food treating agent) of the present invention applied to the object to be treated varies depending on the kind of the object to be treated, the treatment method, etc., and cannot be specified unconditionally. Alternatively, when applied to or sprayed on the cut surface, the amount (total amount) of the sulfide compound (allylmethyltrisulfide, dimethyldisulfide, dimethyltetrasulfide) contained in the treatment liquid used for the application or spraying is 1 to 10,000 μg. / ml, preferably 1-100 μg / ml.

  Moreover, when immersing food, the amount (total amount) of sulfide compounds (allylmethyltrisulfide, dimethyldisulfide, dimethyltetrasulfide) contained in the solution used for the immersion treatment is 1 to 10,000 μg / ml. Preferably, a ratio of 10 to 1,000 μg / ml can be exemplified. Also when adding to edible fats and oils, it can be added at the same ratio as above.

  Furthermore, when an acrylamide formation inhibitor is added to and mixed with food, the total amount of sulfide compounds (allylmethyltrisulfide, dimethyldisulfide, dimethyltetrasulfide) in the final processed product is 1 μg / ml or more, preferably 2 μg / ml or more. An amount that can be included in a proportion can be blended. The upper limit is not particularly limited, but is usually 10,000 μg / ml, preferably 2,000 μg / ml.

  Moreover, this invention provides the foodstuff by which the production | generation of acrylamide is suppressed by processing with the said acrylamide production | generation inhibitor. The food is processed with the acrylamide production inhibitor and is not particularly limited as long as it has the effects of the present invention.

  For example, foods that are heated or oiled, foods such as retort food (sealed packaged food) or bento that is reheated with a range or hot water when eating, and frozen food that is cooked and eaten are widely covered. Can do.

  Specific examples of foods targeted by the present invention include fried foods (French fries, potato chips, fried potatoes, corn snacks), sweet chestnuts, bean confectionery, waffles, karinto, rice crackers, crackers, cereals, wheat koji, almonds , Pretzels, cookies, biscuits and other sweets; croquettes, tonkatsu, fried potatoes, dumplings, spring rolls and other processed foods (oiled foods), sandwiches with oily food sandwiched in bread; stew, curry, curry powder Curry food, risotto, pasta and other retort food: burnt rice balls and rice with burnt eyes; pork, seafood, vegetables and other noodles with food (food fried kitsune udon, nagasaki champon noodles, udon, cold noodles, Buckwheat noodles, instant oil noodles, ramen, etc.); stir-fried vegetables and rice Chinese rice bowl, fried rice, etc.); foods seasoned with soy sauce, vegetables, grilled foods and fruits in ovens (chicken, turkey); various side dishes such as vegetable tempura, deep-fried fish and tempura of various ingredients Examples of preferred beverages for roasting such as barley, bento, barley tea, roasted tea, and coffee beverages. In addition, the above is only an example, and does not mean that it can be applied only to these foods, and can be applied to other foods.

  Hereinafter, the content of the present invention will be specifically described with reference to the following examples. However, the present invention is not limited to these.

Example 1 Preparation and Analysis of Onion Oil (Onion Steam Distillation Extract) An onion (domestic product), a lily family plant, was washed with water and then pulverized with a cutter. While cooling the azeotropic essential oil components, onion oil was obtained by extraction and purification. The onion oil obtained is an essential oil with a peculiar pungent odor of light yellow to brown color, specific gravity 0.900 to 1.150 (pycnometer), refractive index 1.500 to 1.600 (upe refractometer), sulfur content 44.0 to 54.0% ( Flask combustion method) onion oil (specific gravity 1.062, refractive index 1.54, sulfur content 49.6%, flash point 30 ° C.). This onion oil was almost composed of essential oil components, and it was confirmed by gas chromatography mass spectrometry (GC-MS analysis) that allyl methyl trisulfide, dimethyl tetrasulfide, and dimethyl disulfide as sulfide compounds were contained therein.

The measurement conditions for GC-MS analysis were as follows.
<Measurement conditions for GC-MS analysis>
Equipment used: HP6890GC, HP5973MS System column: J & W DB-WAX capillary 60.0mm × 250μm × 0.25μm
Temperature: Start temperature 50 ° C for 5 minutes (3 ° C / min increase) → 220 ° C (75 min)
Injection volume: 1 μl-splitless.

Example 2
In Example 1, the acrylamide production inhibitory effect by the sulfide compounds (allyl methyl trisulfide, dimethyl tetrasulfide, and dimethyl disulfide) found in onion oil was investigated by GC-MS analysis. Specifically, frozen potatoes (square cutting type having a length of about 5 cm and a cut surface of about 8 mm) are oiled with an oil containing the above-mentioned sulfide compound in a predetermined amount, and the sulfide compound for acrylamide production by the oil is prepared. The inhibitory effect was investigated.

1. Preparation of oil sample Each single sample of sulfide compound found in onion oil by GC-MS analysis in Example 1:
(1) Allylmethyl trisulfide (Sample 1, Saneigen FFI Co., Ltd.)
(2) Dimethyltetrasulfide (Sample 2, Saneigen FFI Co., Ltd.) and
(3) Dimethyl disulfide (Sample 3, manufactured by San-Ei Gen FFI)
Is added to 100 ml of edible salad oil (rapeseed oil, manufactured by Nisshin Oilio Co., Ltd.). It was added to 1000 g (made by Kiyooi Rio Co., Ltd.) and used as an experimental oil for oil frying.

  For comparison, (4) (±) -α-tocopherol (comparative sample 1: Wako Pure Chemical Industries, purity 98% or more, density (20 ° C.) 0.950 g / ml), (5) butylhydroxyanisole (BHA) ) (Comparative sample 2: Kishida Chemical Co., 99% purity, reagent grade 1) and (6) Butylhydroxytoluene (BHT) (Comparative sample 3: Wako Pure Chemical Industries, purity 98%, reagent) These were added to 1000 g of edible salad oil (mixed oil of soybean and rapeseed, manufactured by Nisshin Oilio Co., Ltd.) and used as a comparative oil for oil. Further, as a control (control oil), 1000 g of edible salad oil (mixed oil of soybean and rapeseed, manufactured by Nisshin Oilio Co., Ltd.) without any addition was prepared.

2. Potato oil butter Using 1000 g each of the oils prepared in the above (experiment oil, comparative oil, control oil), 100 g of frozen french fries were cooked (cooked (180 ° C., 2 minutes)). Immediately after oiling, the potato was taken out and cooled at room temperature.

  Next, the amount of acrylamide produced in potato was measured using the following method, and the acrylamide production inhibitory effect of each sulfide compound was evaluated from the measured value (E. Tareke et al: Chem. Res. Toxicol., No. 13, 517-522 (2000), A. Arikawa et al: Bunseki kagaku, No. 29, T33-T38 (1980), L. Castle et al: J. Agric. Food Chem., No. 41, 1261 -1263 (1993)).

3. Evaluation of Acrylamide Production Suppressing Effect The amount of acrylamide produced in potato is measured by first crushing the oily potato, pretreating the obtained crushed potato as it is by the following steps, and then subjecting it to GC-MS analysis. Was carried out.

(1) Pretreatment method (i) Crushing and homogenization treatment process The sample is crushed with a food processor. Weigh 10 g from the crushed sample and place it in a No. 1 centrifuge tube (stainless steel). 200 ml of purified water and 100 μl of internal standard substance (acrylamide 1,2,3-13C, manufactured by Cambrigde Isotope Laboratories, hereinafter referred to as “IST”) are added to this, shaken well, and then left for 0.5 to 1 hour. Inflate. Next, homogenizer is used to homogenize the clothing sample (to scale 4; 40-50 seconds). Be careful not to generate heat.

(Ii) Centrifugation process The clothing sample homogenized above is centrifuged using a refrigerated centrifuge (6,000 rpm, 10 mins, and 4 ° C.). 20 ml is sampled from the obtained supernatant and transferred to a centrifuge tube for rotor NO.3.

(Iii) Degreasing step 10 ml of hexane is added to 20 ml of the above supernatant, shaken at room temperature for 5 minutes using a shaker, and then centrifuged (8,000 rpm, 10 mins, 5 ° C.). Remove the hexane layer and the emulsion (emulsion layer) at the interface between the water layer and the hexane layer with a Pasteur pipette, add 10 ml of hexane again, and shake for 5 minutes. Again, centrifuge under the same conditions as above to remove the hexane layer and the emulsion layer. Transfer 5 ml of the defatted sample solution to a 50 ml brown stopper bottle.

(Iv) Bromination step 5 ml of each sample solution transferred to the brown glass stopper bottle is cooled in a water bath, and about 0.5 ml of concentrated sulfuric acid is added thereto and stirred. At this time, using a capillary, it is confirmed that the pH is 1.0 or less with a pH test paper. Next, add about 10 g of potassium bromide and stir with a small mixer. Then add about 6 ml (3 ml × 2) of 0.1M potassium bromate in two portions (Note: At this time, it turns yellow). Leave in a refrigerator (4 ° C.) for about 12 hours.

(V) Debromination step To each sample solution after bromination, 1 mol sodium thiosulfate solution is added until the yellowish brown color of bromine disappears (about 2 ml) to decompose excess bromine. The sample solution is then transferred to a 100 ml separatory funnel. At this time, 5 ml of ethyl acetate is added to the brown stopper bottle containing the sample solution to wash it, and it is transferred to the separating funnel. This is repeated three times (total amount of ethyl acetate: 15 ml). Next, after degassing, shake with a separatory funnel for 5 minutes. The resulting aqueous layer is transferred to the original brown stopper bottle, and the ethyl acetate layer is transferred to a 100 ml Erlenmeyer flask. The above extraction operation is repeated for the aqueous layer, and the ethyl acetate layer is collected (total amount of ethyl acetate: 15 ml + 15 ml = 30 ml). Add about 3 spoons (standard) of anhydrous sodium sulfate to the collected ethyl acetate layer. This is filtered using fold-folded filter paper No. 7 spread on the funnel, the container is co-washed with ethyl acetate (3 ml × 3 times), and all the collected filtrate is transferred to a 50 ml eggplant flask. The ethyl acetate layer is distilled off using a rotary evaporator (about 40 ° C. setting). When the amount of the sample solution decreases (1-2 ml), the eggplant flask is removed from the evaporator and the solvent is blown off under a nitrogen stream. Next, 1 ml of 20% acetone-containing hexane and 20 μl of triethylamine are added to the obtained residue and dehydrobrominated (Note: acrylamide is brominated with a solution of potassium bromide and potassium bromate under acidic conditions, and dibromo Derivative (referred to as dibromopropionamide, ie acrylamide with two bromines attached).

  Excess bromine is eliminated by sodium thiosulfate, and the resulting dibromo derivative is extracted with ethyl acetate. A monobromo derivative (monobromopropionamide, that is, acrylamide to which one bromine is bonded) obtained by adding triethylamine to this to desorb one bromine and dehydrobromating is obtained by a gas chromatograph mass spectrometer (GC- Analyze with MS analyzer).

(2) GC-MS analysis The GC-MS analysis of said monobromo derivative production amount was performed on condition of the following.
Equipment: GC 3800 (Varian), MS Saturn2000 (Varian)
Column: DB-5msitd (Varian), 0.25mmi.d. × 30m
Injection volume: 1 μl, 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 1.

上記結果から、本発明のスルフィド化合物（アリルメチルトリスルフィド、ジメチルテトラスルフィド、ジメチルジスルフィド）はいずれも、油ちょうによって生じる食品のアクリルアミドの生成に対して有意に抑制効果を備えていることがわかった。中でも特にアリルメチルトリスルフィドは、食品のアクリルアミドの生成に対して極めて高い抑制効果を発揮することがわかった。

From the above results, it was found that all of the sulfide compounds of the present invention (allylmethyltrisulfide, dimethyltetrasulfide, dimethyldisulfide) have a significant inhibitory effect on the production of acrylamide in foods produced by oil-frying. . In particular, it was found that allyl methyl trisulfide exerts an extremely high inhibitory effect on the production of acrylamide in foods.

Example 3 Onion extract prepared by supercritical extraction 1600 g of fresh onion (domestic) was washed with water, pulverized with a cutter, and filtered with a filter cloth to obtain about 400 g of a slightly pale yellow clear onion juice. (1600 g of crushed onion was used). Of the prepared onion juice, 190 ml (for 760 g of onion) was added and mixed with 60 ml of 95% ethanol (water-containing ethanol) (onion: water-containing ethanol = 38: 3). The prepared onion-containing ethanol solution (250 ml) was filled in an extraction tank of a supercritical extraction system, and 700 L of supercritical carbon dioxide adjusted to a pressure of 17.5 MPa and a temperature of 50 ° C. was introduced. After introducing carbon dioxide, hold it as it is for 25 minutes, then open the tank using the pressure control valve while adjusting the temperature, release carbon dioxide into the separation tank, and turn onion supercritical CO ₂ extract 50g Was collected from the sample collection port (for 760 g of onion). The yield of the obtained supercritical CO ₂ extract (weight ratio of the extract to the weight of raw onion used) was 6.6%. It was confirmed that the sulfide compound (allylmethyltrisulfide, dimethyltetrasulfide, dimethyldisulfide) of the present invention was contained therein.

Example 4
Allyl isothiocyanate (manufactured by Saneigen FFI, MW = 99.15, purity 95%, containing 1 sulfur) contained in Brassica radish by the same method as in Example 2 Addition amount, the same applies hereinafter)) and 10 ppm each of its precursor allyl isothiocyanate glycoside and glucosinolate (Sinigrin, Wako Pure Chemical Industries, MW = 359.37, 1 sulfur, reagent) I fried French fries. The content of acrylamide found in the obtained french fries was 234 ppb and 249 ppb, and it was found that the production of acrylamide was suppressed to about one half compared to the blank 505 ppb.

Example 5
The oil prepared by adding 10 ppm of the onion supercritical extract prepared in Example 3 to 1000 g of edible oil (Nisshin Oilio, rapeseed oil) was used as an experimental oil for oil cooking in the same manner as in Example 2. The suppression effect of acrylamide formation of the onion supercritical extract was investigated. As a result, the content of acrylamide contained in the obtained potato chips was 484 ppb, showing an inhibitory effect of about 23.4% compared to 632 ppb in the blank (control group). Further, quercetin (reagent, Sigma, MW = 338.3, dihydrate) was used in the same manner as in Example 2 to examine the inhibitory effect of quercetin on acrylamide formation. As a result, the content of acrylamide contained in the obtained potato chips was 504 ppb, which was about 20% less effective than the blank (control group) 632 ppb.

  Moreover, it was confirmed by HPLC mass spectrometry that the supercritical extract of onion contains a quercetin glycoside (for example, glucose bound at position 3). Therefore, by using a sulfide compound (allylmethyltrisulfide, dimethyltetrasulfide, dimethyldisulfide, etc.) or a plant fraction containing the compound (for example, a supercritical extract of onion) and quercetin or a glycoside thereof. It was suggested that the suppression effect of acrylamide formation was improved.

Example 6
The oil prepared by adding 10 ppm of the onion supercritical extract prepared in Example 3 to 1000 g of edible oil (Nisshin Oilio, rapeseed oil) was used as an experimental oil for oil cooking in the same manner as in Example 2. The suppression effect of acrylamide formation of the onion supercritical extract was investigated. As a result, the content of acrylamide contained in the oiled french fries was 444 ppb, which showed an inhibitory effect of about 20% compared to 558 ppb of the blank (control group). The fried potatoes made with oil were tasty and sweet.

  In addition, oil prepared by adding methylpropyl trisulfide, methylpropyl disulfide, and dimethyl trisulfide (each 10ppm) contained in onion to edible oil (Nisshin Oilio, rapeseed oil) 1000g was used as an experimental oil for oil. In the same manner as in Example 2, the effect of suppressing the acrylamide formation of each sulfide compound was examined. As a result, the contents of acrylamide contained in the oiled french fries were 250 ppb, 432 ppb, and 491 ppb, respectively. That is, against the blank (control group) 625 ppb, methylpropyl trisulfide showed an inhibitory effect of about 60%, methylpropyl disulfide showed an inhibitory effect of about 30%, and dimethyltrisulfide showed an inhibitory effect of about 21%. .

  In addition, when potato tempura with a garment is oiled instead of fries, the test oil containing methylpropyl disulfide can be reduced to a ratio of about 7% (38 ppb / 509 ppb blank) relative to the blank. (Acrylamide production inhibitory effect: 93%).

  In addition, when methylpropyl trisulfide having one more sulfur in the sulfide was used, a better acrylamide production inhibitory effect was obtained than methylpropyl disulfide. This suggests that the influence of sulfur is reflected in the suppression of acrylamide.

Example 7
In the same manner as in Example 2, using oil prepared by adding 1000 g of onion oil (10 ppm, 20 ppm) prepared in Example 1 to 1000 g of edible oil (Nisshin Oilio, rapeseed oil) as an experimental oil for oil frying. Thus, the effect of suppressing the acrylamide production of the onion oil was examined. As a result, the content of acrylamide in the oiled fries decreased to 476 ppb (when using 10 ppm of oil) and 281 ppb (when using 20 ppm of oil) compared to the blank (control) 539 ppb, and the concentration added was increased. It was found that the effect of suppressing acrylamide generation is increased by making it.

In addition, the fries obtained by the oil treatment had a good taste, had no scent peculiar to onion oil, and had a good flavor.

Claims (7)

An acrylamide production inhibitor for foods containing, as an active ingredient, at least one sulfide compound selected from the group consisting of allyl methyl trisulfide, dimethyl tetrasulfide, and dimethyl disulfide. The acrylamide production inhibitor according to claim 1, wherein the sulfide compound is allylmethyltrisulfide. The acrylamide production inhibitor according to claim 1 or 2, comprising an allylmethyl trisulfide-containing fraction, a dimethyltetrasulfide-containing fraction, or a dimethyldisulfide-containing fraction of a lily family as an active ingredient. The acrylamide production inhibitor according to claim 3, wherein the allylmethyltrisulfide-containing fraction, dimethyltetrasulfide-containing fraction, or dimethyldisulfide-containing fraction is an essential oil fraction of a lily family plant. The acrylamide production inhibitor according to claim 3 or 4, wherein the lily family plant is one or more selected from the group consisting of onion, leek, garlic, leek, raccoon, scallion, and leek. The food processing agent containing the acrylamide production | generation inhibitor of any one of Claims 1 thru | or 5. Including the step of adding the acrylamide production inhibitor according to any one of claims 1 to 5 or the food treating agent according to claim 6 to oil at the time of oiling or adhering to the surface of food. A method for suppressing acrylamide formation in foods.