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CN1013336B - Process for preparing alpha-maltose crystals - Google Patents

Process for preparing alpha-maltose crystals

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Publication number
CN1013336B
CN1013336B CN85105158A CN85105158A CN1013336B CN 1013336 B CN1013336 B CN 1013336B CN 85105158 A CN85105158 A CN 85105158A CN 85105158 A CN85105158 A CN 85105158A CN 1013336 B CN1013336 B CN 1013336B
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China
Prior art keywords
maltose
crystalline alpha
alpha
crystalline
preparation
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CN85105158A
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CN85105158A (en
Inventor
三桥正和
堺修造
三宅俊雄
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Hayashibara Seibutsu Kagaku Kenkyujo KK
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Hayashibara Seibutsu Kagaku Kenkyujo KK
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Publication of CN85105158A publication Critical patent/CN85105158A/en
Publication of CN1013336B publication Critical patent/CN1013336B/en
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  • Saccharide Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Confectionery (AREA)
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Abstract

A process for producing crystalline α -maltose containing 55% or more of α -maltose isomer, which comprises preparing a high concentration syrup containing less than 10% (W/W) of water from high purity maltose containing 85% or more; crystallizing alpha-maltose from the syrup at a temperature between 50-130 ℃ in the presence of seed crystals; crystalline alpha-maltose containing 55% or more of alpha-maltose isomer is recovered. The solubility and dispersibility of the alpha-maltose crystal in the aqueous solution are better than those of the beta-crystalline maltose, and the alpha-crystalline maltose is a suitable maltose material for food and pharmacy. Convenient parenteral high nutrition products with high resistance to browning and spoilage are also prepared using alpha-maltose crystals.

Description

Method of preparation crystalline alpha-maltose
The present invention relates to the crystallization of a kind of d-maltose, and its production and application.Be particularly related to and a kind ofly contain 55% or preparation crystalline alpha-maltose and its production and the application of more α-maltose isomers.
Weight percent " part " the used herein speech that the outer unless stated otherwise percentage ratio of usefulness here is based on drying solid weight also is meant weight." α-maltose isomer content " is meant the maltose of optical siomerism α configuration and the percentage ratio ratio of whole maltose, all is based on the weight percentage of drying solid.
Sucrose is used for food in large quantities, but the shortcoming of sucrose is too sweet, so it is one of inducement of carious tooth, huge uptake sucrose also can improve the level of blood cholesterol.
For overcoming these shortcomings of sucrose, non-sucrose sweeting agent has been used in suggestion in recent years.Particularly become " SUNMALT " of commodity.It is a kind of crystal of Powdered beta-maltose hydrate, is Hayashibara company limited (Okayama, product Japan).The crystallization of this beta-maltose hydrate does not have sucrose sweet, compare with sucrose to be difficult for causing carious tooth, and the user feels that fragrance is very good yet.Therefore, the crystallization of a large amount of beta-maltose hydrates is used as the sweeting agent of New Times.Yet beta-maltose hydrate crystalline is used and to be made food-processing complicated and difficult more, and up to the present, using maltose, to process the low as chocolate food of water content be unusual difficulty.As at (the 3rd section, 2-5 is capable) described in the Japanese patent laid-open publication gazette 26,303/83 thus since the maltose overslaugh chocolate processing it in fact be not used in chocolate production.And for example (the 3rd section inferior horn 11-12 is capable) described in the Japanese publication 31,650/84, maltose should not be used for making chocolate.In order to attempt to overcome these shortcomings, Japan's publication 26,303/83 suggestion crystallization of sucrose and beta-maltose hydrate crystalline powder mixture, for example " SUMALT ", Japanese Laid-Open Patent Application 31,650/84 has compared several Powdered beta-maltose hydrate crystalline holds oily power, and suggestion is held oily power less than 80 product with a kind of.Yet, both made according to these suggestions, it is still very difficult to prepare chocolate with the crystallization of Powdered beta-maltose hydrate.Therefore, also not commercialization as yet so far of this chocolate.
We find the low food of water content is processed in the crystallization of powder application powder beta-maltose hydrate, and why very difficult major cause is because it causes the efficient of the course of processing to reduce.Because this course of processing mainly comprises a step, be about to Powdered sugared crystallization and pulverize evenly or sugar is distributed in the food with other food raw materials and go.This step is by finishing such as pulverizing, divide, grind, rub up, mix supervisor.In addition, in this step course of processing, do not allow in the too many water-soluble medium of Powdered sugared crystallization.Therefore the crystallization of Powdered beta-maltose hydrate makes and obstacle occurred in these step.For example increase viscosity, formed some insoluble Icing Sugar groups (damo-day transliteration); Thereby skidding (Suberi-gensho-day transliteration) has appearred; These obstacles cause Powdered beta-maltose hydrate crystalline pulverizing and are uniformly dispersed very difficult.
With the crystallization of Powdered beta-maltose hydrate,, must use effective and complicated method and beta-maltose hydrate powder is joined in the processed food equably go during the high food of processing water content because that it is dissolved in the moist food is slow.For example: making the cream process, just must be first the crystallization of Powdered beta-maltose hydrate and sucrose be dissolved in and makes sugar soln in the less water, under agitation mixing then with the butter of hitting.Making marsh-mallow (mashmo-llow) process, also must earlier Powdered beta-maltose hydrate crystallization and the sucrose of solution in less water made sugar soln, beating with the gelatinum limit heating edge that is dissolved in advance in the hot water then.When making " Kyuhi(rice cake) ", also, make liquid glucose, then with gelationus starch paste Hybrid Heating earlier with less water dissolved powders shape beta-maltose hydrate crystallization and sucrose.Making a kind of beans cake also is as above to manufacture earlier liquid glucose, then itself and " nama-an " (day transliteration, the meaning are to give birth to beans pudding) is mixed, and heating concentrates and forms.In brewing wine flavoring " ZOZYO-Shu " (" a kind of artificial rice wine ") process, earlier 30%(V/V) alcohol is placed in the bucket, add crystallization of Powdered beta-maltose hydrate and condiment again, mix to stir 30 minutes or (2) first standing over night and then stir with a wooden stick (1) then.
Combine as above-mentioned, develop a kind of newly be easy to dissolve and the novel maltose product that is dispersed in the foodstuffs material is badly in need of.Make parenteral convenient high-nutrition food and need this maltose too.
Parenteral high-nutrition food is used for intravenous injection or intubate feeds, and is widely used in the people that can not normally take food as patient, convalescent patient or weakly people.In general inevitable shortcoming is arranged is container to the parenteral high-nutrition food, and packing and transportation are expensive and must be kept at low temperature or validity period is limited.This is because its effective constituent causes change or rotten easily.For addressing these problems, adopted recently to make things convenient for stomach peripheral hyperalimentation food.As Japanese Laid-Open Patent Application 61,310/81 or 128,711/81 the narration, in convenient parenteral high-nutrition food, generally all adopt glucose as caloric source.Though glucose has its advantage that can directly be utilized in vivo, its shortcoming is that each intake can only be supplied with lower calorie because a small amount of glucose (5% W/W) has just reached isotonic concentration.
For overcoming this shortcoming of glucose, what Japanese Laid-Open Patent Application 20174/79 suggestion manufacturing contained maltose makes things convenient for stomach peripheral hyperalimentation food.The osmotic pressure that obtains with the maltose with the glucose same amount is half of glucose.Thereby, because the maltose solution energy supply Duo one times of calorie than glucose solution and osmotic pressure is identical, thus with maltose just than glucose favourable must.According to making things convenient for the big quantity research of parenteral high-nutrition food, we are surprised to find that because beta-maltose hydrate crystalline solubleness is low and highly unstable when preserving in container, often cause and become rotten and rotten, it is unfavorable being used in the food, just can not use the crystallization of beta-maltose hydrate so will prepare the parenteral high-nutrition food of satisfied convenient.
We have studied these shortcomings that much overcome maltose in common food and the medicine, found that, with crystalline alpha-maltose, particularly contain 55% or the preparation crystalline alpha-maltose of above α-maltose isomer just can overcome these shortcomings.
Yet preparation crystalline alpha-maltose had both made as chemical reagent and all can't obtain, let alone edible.
People such as J.E.Hodge have reported the α/β maltose mixture (today cereal science, 17 volumes, 7 phases, 180-188 page or leaf, 1972Cereal Sciene Today) of 3: 1 or 4: 1.
Want to make this crystalline composites, the author advises using following method:
(1) crystalline beta-maltose hydrate (fusing point is 121-125 ℃) was heated one day under 120 ℃ of normal atmosphere, make it change into preparation crystalline alpha-maltose;
(2) will be from 60%(W/W) viscous syrup that maltose solution dewaters and obtains in the time of 80-100 ℃, as carrying out crystallization in the presence of the seed, use methanol wash at crystal, refilter, obtain output and be 70% preparation crystalline alpha-maltose.
(3) amorphous maltose particle is refluxed a night in anhydrous maltose or anhydrous isopropyl alcohol, obtain preparation crystalline alpha-maltose.
The α that method (1) obtains-the maltose color is not good enough, particularly according to this sugared 30%(W/W) aqueous solution is in the cuvette of 10 centimetres (cm), thereby 420 millimicrons and 720 millimicrons are located to measure the photoabsorption poor (A420-720) that dullness calculates, and the colourity that has of this sugar is 3.5.We have confirmed that this colourity is approximately 50 times of beta-maltose hydrate crystalline.Thereby this preparation crystalline alpha-maltose can not be as the sweeting agent on the market.This method also just can not be used for industrial production.
It is lower but also consume a large amount of methyl alcohol that method (2) obtains the output of preparation crystalline alpha-maltose.From production cost, food sanitation and fire prevention equal angles, this method also is unsuitable on industrial production and uses.
From production cost, food sanitation and fire prevention equal angles, method (3) can not be used for large-scale commercial production, because it need consume a large amount of organic solvents.
For setting up the technology of a cover industrial production preparation crystalline alpha-maltose, we have studied the production method of the Powdered preparation crystalline alpha-maltose of the low colourity of a lot of methods, particularly good quality and high output, and it is in the application of food and pharmaceutical industry.
As a result, we find with the following method this preparation crystalline alpha-maltose that is easy to get, this method comprise earlier with contain 85% or more the high malt sugar high purity maltose prepare water content and be lower than 10%(W/W) high-density syrup; In 50-130 ℃ of temperature range, have in the presence of the seed crystalline again, go out α-maltose from this syrup crystallization; Reclaim at last and contain 55% or the preparation crystalline alpha-maltose of higher α-maltose isomer.
We have confirmed that this preparation crystalline alpha-maltose is easily with other foodstuffs material mixing abrasive dust or be distributed in the foodstuffs material equably and go, influence not and change common food-processing step, and can easily produce the high-quality acat of random control sweet taste with this preparation crystalline alpha-maltose.
We also find this preparation crystalline alpha-maltose tool following properties:
(1) than the easier dissolving of beta-maltose hydrate crystallization, in the solubleness very high (even also easily dissolving at low temperatures) of water system.
(2) its oleophylic and lipophilic characteristic also are better than the beta-maltose hydrate.
(3) browning and/or rotten not, more stable when being kept in the closed container, also highly stable through prolonged preservation.
We confirm that these characteristics help making special medicinal ingredients, particularly make things convenient for stomach peripheral hyperalimentation food, hope on the food of copying, can balance contain high calorie oil and (or) food that makes things convenient for the stomach peripheral hyperalimentation of fat, after adding water medium simultaneously, can make the very fast dissolving of this ready-to-eat and disperse and be easy to form utilizable latex in vivo.
Fig. 1 is the X-ray diffractogram that contains the unsetting Icing Sugar of 48.0% α-maltose.
Fig. 2 is the X-ray diffractogram that contains 55.6% preparation crystalline alpha-maltose powder.
Fig. 3 is the X-ray diffractogram that contains 61.4% preparation crystalline alpha-maltose powder.
Fig. 4 is the X-ray diffractogram that contains 68.7% preparation crystalline alpha-maltose powder.
Fig. 5 is the X-ray diffractogram that contains 14.2% preparation crystalline alpha-maltose powder.
Fig. 6 be " the Powdered beta-maltose hydrate of MALTOSE HHH(crystalline commodity) X-ray diffractogram.
The better narration of embodiment
The maltose raw material that is used to produce preparation crystalline alpha-maltose is to contain 85% or more highly purified maltose.This maltose raw material can be a commercial beta-maltose hydrate or by with the preparation of common mode starch saccharification.For example: Japanese publication 11,437/81 or 17,078/81 has disclosed the method for producing high purity maltose, and wherein the starch of agglutination or liquefaction is separated maltose by β-starch hydrolysis again from the high-molecular weight dextrin; Japan publication 13,089/72 and 3,938/84 act on the starch of glue or liquefaction with beta-amylase and starch-debranching enzyme such as isoamylase or side chain enzyme etc.
In Japanese publication 28,153/81; 3,356/82; Or 28,154/81st, that discloses passes through a kind of specific enzymes effect hydrolysis can increase high purity maltose such as polysaccharide impurity such as trisaccharide maltoses output.In addition, the strong-acid cation-exchange resin column chromatography that has disclosed in Japanese publication 23,799/83 in order to salt form comes separating high-purity maltose to remove polysaccharide impurity.The method of the available fixed bed of this separation, moving-bed or imitation moving-bed.
To contain 85% or more highly purified maltose be condensed into water content and be lower than 10% syrup, preferably water content is higher than 2%(W/W) be lower than 9.5%, add the crystallization in the time of about 50-130 ℃ of 0.01-20% α-maltose seed crystal then, can obtain preparation crystalline alpha-maltose.
If we find that with water content be 10% or more during high-purity maltose syrup, it is non-crystallizable just to have a certain amount of α-maltose: particularly, with water content 12% or be higher than 12% and be lower than 25%(W/W again) α-malt syrup the time, preparation crystalline alpha-maltose seed instability, may dissolve, beta-maltose hydrate then crystallization goes out.We also find to be lower than 2%(W/W with water content) syrup can make crystallization slow excessively.
Better the crystalline optimal temperature is 50-130 ℃, preferably 60-120 ℃.It is very slow to be lower than 50 ℃ of then crystallization processes, thereby unfavorable to industrial production.Temperature is higher than 130 ℃ and also is unfavorable for crystallization, and the crystallization velocity of α-maltose also can cause the preparation crystalline alpha-maltose color burn because high temperature can slow down.
Therefore, the method according to this invention mainly comprise make water content be lower than 10%(W/W) high-purity maltose syrup crystal is being arranged as carrying out the crystalline step in the presence of the seed under 50-130 ℃.
Prepare this highly purified malt syrup can with contain 85% or more the commodity beta-maltose hydrate crystallization of high malt sugar be dissolved in the small portion water also can by obtain from starch saccharification containing 85% or more the high purity maltose aqueous solution of high malt sugar concentrate in a vacuum.In addition, can also be water content 10%(W/W) or be higher than 10% and be lower than 35% high purity maltose again and become water content to be lower than 10% syrup droplet with proper method such as spray drying method for preparation.
Generally come crystalline alpha-maltose to need 0.001% or be higher than 0.001% but be lower than 100% preparation crystalline alpha-maltose as seed from high-purity maltose syrup, best seed crystal amount is 0.1% or is higher than 0.1% but be lower than 20%.For example, want the available water content of crystalline alpha-maltose (1) to be lower than 10%(W/W) high-purity maltose syrup mix with α-maltose seed nuclei of crystallization, or (2) are 10%(W/W with water content) or be higher than 10% but when being lower than 20% high-purity maltose syrup, it and seed crystallized mixed are lower than 10% syrup droplet but make water content by spraying drying before the seed crystallization does not dissolve away as yet.And when using water content 10%(W/W) or be higher than 10% when being lower than 35% syrup, just must be prepared into water content earlier and be lower than 10% droplet.Thereby just contacting crystallization with seed crystal then is crystalline alpha-maltose.
Slight pressurization can be quickened the preparation crystalline alpha-maltose process, particularly crystallization begin or crystallisation process in use 5kg/cm 2Or higher pressure helps crystallization most.In pelletization, pressure boost is very favorable when crystalline α-maltose is pulverized by pressurization or compression.
We find to make the crystallization suspension dehydration also to help quickening the preparation crystalline alpha-maltose process.Crystallization suspension is left standstill or when mobile, this dehydration can be carried out under decompression or the pressurized conditions at normal pressure.
The technology of these accelerate crystallisations has shortened 4/5-2/5 and has obtained containing 55% or the required time of higher α-maltose isomer.And then these technologies have improved the efficient of producing preparation crystalline alpha-maltose, have reduced the colourity of crystalline alpha-maltose widely.Therefore, these technologies are very favourable to the high-quality crystalline alpha-maltose of industrial production.These technologies are used in combination also can be more favourable.Highly purified malt syrup crystallization as stated above for example: be lower than 10%(W/W) with water content, the crystallization suspension that obtains further is prepared into any needed shape again, as Powdered, fibrous, block or the like, down dehydration is aging at 50-130 ℃, thereby obtains containing 55% or crystalline alpha-the maltose of higher α-maltose isomer.
As required can be at 50-100 ℃ of continuous ageing 0.1-24 hour, also can be lower than 130 ℃ of following continuous ageing 0.5-18 hours being higher than 100 ℃.We find under the intensive condition aging, and for example the high temperature of the long period color that can increase crystalline alpha-maltose makes it be not suitable for selling.Pressurization and (or) dehydration helps shortening the crystallization that digestion time can also be quickened α-maltose.
Contain 55% or the crystalline alpha-maltose of higher α-maltose isomer generally can make such as desired forms such as Powdered, particulate state with the technology that is fit to.These technologies comprise granulating or piece, become powder, spraying drying and liquefied bed granulating.
High-purity malt syrup for example: in that to be extruded into the particulate process be that water content is lower than 10%(W/W) and α-maltose seed crystallization are added in the granulator then at 50-130 ℃ of preparation crystalline alpha-maltose suspension that mixes to obtain containing more than 48%.Particle suspension or granular solids obtain moisture 55% or the Powdered crystalline alpha-maltose of higher α-maltose isomer in that 50-130 ℃ of dehydration is aging.Another kind method is water content to be lower than 10% high-purity malt syrup feeding earlier squeeze the grain machine and not seed addition crystallization; make the syrup droplet; it is contacted with the seed crystallization, and dehydration is aging down at 50-130 ℃ again, obtains a kind of and above-mentioned similar Powdered crystalline alpha-maltose.
And for example in becoming piece or powder process, will moisturely be lower than high-purity malt syrup feeding crystallizer of 10% earlier, 50-130 ℃ and α-maltose seed crystallized mixed to impel crystallization.Gained is contained α-maltose isomer be higher than 48% crystalline suspension and pour lead pan into,, solidify 50-130 ℃ of crystallization.The block crystalline solid of gained with digging or hammer is pulverized, through dehydration, is filtered out and contains 55% or the Powdered crystalline alpha-maltose of more α-maltose isomer.
For another example in spray-drying process, moisture 10% or be higher than 10% but be lower than high-purity malt syrup of 20% and α-maltose seed crystallized mixed and make seed crystal be unlikely dissolving by high pressure spray nozzle or rotating-disk spraying drying as early as possible to disappear.Then the last step obtain moisture to be lower than 10% syrup droplet aging 50-130 ℃ of dehydration, obtain containing 55% or the Powdered crystalline alpha-maltose of more α-maltose isomers.
The granulated process of liquefied bed is moisture 15%(W/W for another example) or be higher than 15% and be lower than 35% highly purified malt syrup and spray to crystallization of fluids α-maltose as seed crystal and obtain water content and be lower than 10% syrup droplet, aging it then 50-130 ℃ of time dehydration, obtain containing 55% or the Powdered crystalline alpha-maltose of more α-maltose isomers.
Liquefied bed granulating process is water content 15%(W/W) or be higher than 15% but be lower than 35% high-purity maltose syrup towards liquefaction crystalline alpha-maltose spraying, the latter is as the seed crystallization, thereby obtain water content and be lower than 10(W/W) the syrup droplet, aging 50-130 ℃ of dehydration then, obtain Powdered crystalline alpha-maltose, it contains 55% or higher α-maltose isomer.
A part of α-the maltose that obtains like this can be used for continuing further to produce preparation crystalline alpha-maltose as the seed crystallization.
Contain 55% or the Powdered preparation crystalline alpha-maltose that is higher than α-maltose isomer of 55% be white, tasteless, little sweet, nonhygroscopic, free flowing granule, but with particle shape, size and α-maltose isomer content is variant slightly.The water content of preparation crystalline alpha-maltose is low, generally is lower than 5%(W/W), be preferably lower than 3%(W/W).Fusing point is 130 ℃ or is higher than 130 ℃, is higher than beta-maltose hydrate crystalline fusing point (121-125 ℃) far away.Contain 60% α-maltose isomer or be higher than 60% Powdered maltose crystalline fusing point and be approximately 140 ℃ or be higher than 140 ℃ and its and have and to make the satisfied mobility of people but can not cause unwanted bonding and solidify.
The back will be described preparation crystalline alpha-maltose in detail as food, and the glycogen material of cosmeceutical and reagent etc. is suitable.
Seasonings as sweet food, preparation crystalline alpha-maltose of the present invention can use separately or with such as the starch dust carbohydrate, glucose, isomery carbohydrate, sucrose, honey, maple sugar, sorbyl alcohol, maltol (maltitol), dihydonchauan, stevioside (glucoside), alpha-glucosyl stevioside, and the sweeting agent that obtains by the stem of Momordica grosvenori, glycyrrhizin, thaumatin, L aspartoyl L-phenylalanine methyl ester, asccharin, glycine or L-Ala and (with) additive uses together; Additive such as dextrin, starch or lactose.Powdered preparation crystalline alpha-maltose can be separately or and additive, carrier and (or) tackiness agent makes needed shape according to purposes together, sheet, bar-shaped, tabular, square or the like for example.
We find that a large amount of preparation crystalline alpha-maltoses is instant in a lot of acylate solutions and water.Certainly, preparation crystalline alpha-maltose makes food little sweet, and is soft suitable, smooth, thickness is suitable to contain certain moisture content, can not cause carious tooth again or increase the blood inner cholesterol, the disadvantage that general maltose often has, therefore, preparation crystalline alpha-maltose helps making food, makeup and medicine.
Because a large amount of preparation crystalline alpha-maltose can speed in water-soluble or other many solution, therefore it can directly integrate in aqueous food raw material, as the water-sol, in half colloidal sol and the gel, such as with fruit juice, honey, jam, egg, milk, sour milk, gelling starch paste, walnut dew, butter, oleomargarine, flesh of fish sauce, " nama-an " (a kind of living beans sauce), a kind of zymotic soybean paste of miso(Japan), go in the bread etc., these all are used as manufacturing moisture 10% or are higher than 10% processed food.This just shorten and (or) simplified the making step of these processed foods.In obtaining processed food, water is active significantly to be reduced, and the reversed reaction of gelatinize starch component content will postpone when adding starch afterwards.Thereby prolonged the storage life of processed food.
We also find, do not resemble Japanese patent laid-open publication gazette 48,198/77 described Powdered malt syrups, a large amount of preparation crystalline alpha-maltoses in addition can be instant in 40%(V/V) ethanol aqueous solution.Add above-mentioned little sweetly, characteristics such as certain density and viscosity are arranged, make it be well suited for seasoning sugar as alcoholic drinks.Thereby preparation crystalline alpha-maltose is particularly suitable for manufacturing contains Wine, as wine, and artificial sake(sake wine) and " ZOZYO-Shu ".
Yet we are surprised to find that, though preparation crystalline alpha-maltose is a hydroaropic substance.It and oil ﹠ fat have high affinity.This be fit to make such as chewing gum, chocolate, butter flavouring its, and the powdery oil ﹠ fat is dissolved in the powdered flavour of oil, be dissolved in the particulate state tinting material of oil, convenient soup blend is dissolved in the vitamin b6 usp preparation of oil and is dissolved in oily hormone sheet, or unsaturated long-chain fat sheet, this tablet contains such as soya-bean oil, rapeseed oil, mustard oil, sesame oil, Thistle oil, plam oil, theobroma oil, ox (sheep) oil, lard, chicken fat, sea-food oil and the molten material of the sclerosis greasy oil of wet goods; Or oily molten spices is such as tangerine mandarin orange essential oil, flower essential oil, spice oil, spearmint oil, Spearmint Oil 56, cola benevolence extract and coffee extract, oily molten tinting material be such as β-Hu Luobusu, capsochrome, the annotto pigment, chlorophyll or the like, or oil-soluble vitamins such as liver oil, vitamin A, vitamins B 2Lactic acid salt, vitamin-E, vitamin K or D, oily molten hormone such as oestrogenic hormon, Progesterone, male sex hormone or undersaturated higher fatty acid such as linolic acid, linolenic acid, arachidonic acid, eicosapentaenic acid (eicosapentaenoic) and docosahexenoic acid.
Preparation crystalline alpha-maltose little sweet can with tart flavour, saline taste, astringent taste, delicate flavour and the bitter taste harmony of other materials, and itself is highly acidic and heat-proof.Therefore, preparation crystalline alpha-maltose generally is well suited for being used for making sweet food except that above-mentioned special purpose, thereby improves the taste of food.
Preparation crystalline alpha-maltose can be used to make condiment, as: soy sauce, powdery soy sauce, zymotic soybean paste (miso), the powdery zymotic soybean paste, " moromi(rough cake) " " hishio(bacon) ", " the fish meal of a furikake(seasoning) ", salad oil, Japanese soy sauce, vinegar, " sanbaizu(juice that contains rice wine, soybean and vinegar) ", funmatsu-sushi-no-moto(mixing is an available condiment), " chuka-no-moto(Chinese fast food); " juice of a tentsuyu(Japanese Fried Fishes) ", " juice of a mentsuyu(japanese noodles) ", chile sauce, pasta sauce, " yakiniku-no-tare(Japanese barbecue is with watering juice) ", curried volume, instant stewing material, instant soup blend, " dashi-no-moto(dense condiment of speed), mixed spices ", mirin(sweet cake), shin-milin(artificial sweet cake) have tea or coffee with sugar or the like, can also increase food sweet taste and quality, be used in such as following Japanese sweet food; " Senbei(rice thin pancake) ", " araremochi(rice cake group) " " okoshi(millet and rice mix the cake that makes) ", " Kyuhi(rice dumpling) " " manju(cookie that presss from both sides beans sauce) " " uiro(sweet rice freezes) ", " an(beans sauce) ", " Yokan(sweet beans freeze) ", " mizuyokan(soft adzuki beans freeze) ", " Kingyoku(yokan); fruit jelly; " paode Castella(steamed sponge cake) " and " the amedama(toffy) " also can do Western sweet food and dessert; as: cookie; biscuit, pancake; cooky, stuffed cake pudding, cream, custard, pop-over muffin, nest VOR cake, steamed sponge cake, fried bagel, chocolate chewing gum, candy and honey; Also can do cold sweet food such as: ice cream and " ice cream that Shurbet(is not with milk "; Syrup such as: " Kajitsu-no-syrup-zuke(candied fruits) " and " Korimitsu(water ice syrup); The cream class is such as batter cake cream (sauce), peanut cream sauce (cream), and fruit is stuck with paste sauce (cream); Processed fruit and vegetables such as jam, marmalade and Syiup-zuke(syrup fruit), " toka(sugar Fruit); Pickled vegetable product such as: the bright pickles radish of " fukujun-zuke(red Kimchi radish), " bettara-zuke(), " the another kind of bright pickles radish of Senmai-zuke(and to flood bubble verdant; Quick pickles and flood the system product, such as " takuan-zuke-nomoto(quick pickles radish) and " hakusai-zuka-no-moto(quick bright pickles white turnip) "; Meat product such as (ham, sausage :) fish flesh prod such as fish, Ham with fish Pork sausage, " kamaboko(Steamed fish cream) ", " chikuwa(fish cream) and " tenpura(Japanese fried food product); " the chinmi(seasonings) " such as " unino-shiokara(Saltwater Sea courage intestines) ", " ika-no-shiokara(salty cuttlefish intestines) ", the sea-tangle of a Su-konbu(processing) " " the dried cuttlefish cutlet of Sakisurume() " and " fugu-no-mirn-boshi(dried seasoning filefish) "; " tsukudani(compression bean product) as adding laver, add edible wild plant, add dried cuttlefish, add fish and add shellfish; Home cooking as " nimame(boils beans), Potato salad and " konbu-maki(one main laminaria volume) milk preparation; Canned and bottled product such as canned meat, fruits and vegetables can; Alcoholic drinks such as artificial rice wine, " Zozyo Shu ", fruit wine and sharp wine for a long time; Soft drink such as coffee, cocoa, fruit juice, carbonated drink, sour milk drink and lactobacteria-containing drink; Snack food product such as assorted pudding fast food, fast pancake, fruit are expected powder, soluble coffee, " mixed fast food of Sokuseki-Shirukol(adzuki-beans soup and rice cake " and fast food soup.
Preparation crystalline alpha-maltose can as feed and domestic animal food directly keeps fowls, poultry domestic animal, family are breeded fish, honeybee, silkworm and fish.
In addition, the all right solid of preparation crystalline alpha-maltose, pasty state or liquid form are as the sweet taste of sweeting agent makeup and medicine, such as: cigar, cigarette, toothpaste, lipstick, lipstick, endo-medicine, tablet, Oils,glyceridic,cod-liver drops, cleaning agent for mouth cavity, Cachou and Collutorium, and the taste that is used to improve these products.
The component that preparation crystalline alpha-maltose is suitable in the parenteral high-nutrition food easy to prepare produces heat.This be because:
(1) because it is very hydrophilic, solubleness is very high in the aqueous solution.
(2) again since it and oily substance high affinity arranged have an intensive emulsifying capacity.
(3) when in the container that is stored in sealing, be not easy very much browning or rotten.
Preparation crystalline alpha-maltose can be added in any step of easily manufactured parenteral high-nutrition food.
Iff needing, can be contained in preparation crystalline alpha-maltose to contain in the container that makes things convenient for the stomach peripheral hyperalimentation easily and prepare for energy supply.If desired nutrition more equilibrated make things convenient for the stomach peripheral hyperalimentation food then to add one or more nutritions again, as other carbohydrates, protein, amino acid, oil, fat, VITAMIN, mineral substance or the like.Can add with crystalline alpha-maltose, can also add one or more additives as microbiotic, hormone, immune-regulating factor, medicine crude extract, antioxidant, tinting material, emulsifying agent, additive or the like.When making things convenient for stomach peripheral hyperalimentation food, be used for injection or blood when rolling over thoroughly, then must and not contain the former raw material that generates heat with the high purity that comprises the preparation crystalline alpha-maltose body.Make things convenient for stomach peripheral hyperalimentation food to be made generally in Powdered or thereby particulate state can be dissolved as early as possible.
Encapsulate the container of fresh preparation, preferably water-proof container can make it preserve the long period.If desired, can bleed to container earlier, inject then such as rare gas elementes such as carbonic acid gas, nitrogen or argon gas.
Make things convenient for the soluble in water or aqueous solution of stomach peripheral hyperalimentation product, also easily be emulsified into the emulsion of normality by water or the aqueous solution, then this solution or emulsion are injected muscle, vein or abdominal cavity with suitable manner, for example: inject in intramuscular injection, vein or the abdominal cavity; Or intubate is in nose, in esophagus or the stomach; Or the personnel selection kidney carries out dialysis in the blood vessel.Because convenient parenteral high nutritious prod is enclosed in and can directly adds water in the water-proof container or the aqueous solution dissolves it in container, so can obtain the parenteral hyperalimentation fluid of liquid easily.When liquid preparation is used for injection or hemodialysis when analysing, the osmotic pressure of preparation can ooze by carefully making things convenient for dissolving stomach peripheral hyperalimentation product to be adjusted to possible grade.
This liquid preparation is very fast can supply with high calorie just because of take in, so it is applicable to the people of normal malabsorption, such as, baby, ill and convalescent after being ill people or the people who after strong training, becomes and become thin.
When carrying out hemodialysis, make things convenient for stomach peripheral hyperalimentation product before usefulness, to be dissolved in to hemodialysis and analyse in the special liquid preparation of usefulness by kidney machine.Comprise that by the hemodialysis supply maltose and nutritive ingredient do not rely on Regular Insulin to the utilization that the waste discharge in the blood is supplied the maltose of blood in the liquid preparation simultaneously.Thereby, make things convenient for stomach peripheral hyperalimentation product to be specially adapted to insulinopenic patient, as: the diabetics.
The present invention will further illustrate by following experiment.
Experiment 1
The comparison of several maltose materials;
Several starchy carbohydrate products commodity of company limited (Japanese Hayashibara) are as raw material in the table I.Syrupy product " MALSTAR R" or " HM-75 " be placed on vacuum-drying in the vaporizer, the product water content is 4.5%(W/W).The crystallization of Powdered beta-maltose hydrate.I.e. " SUNMALT (B)", " MALTOSEH ", " MALTOSE HH ", or " MALTOSE HHH " are dissolved in less water, and heating is placed on vacuum-drying in the vaporizer, the product water content is 4.5%(W/W).
Is above-mentioned gained water content 4.5%(W/W) syrup place crystallizer, add 2% α-maltose seed crystal, this seed crystal is to use 50%(W/W after the crystallization) " MALTOSE HHH " hot alcohol aqueous solution reclaims.(MALTOSE HHH is the high-purity beta-maltose hydrates of a kind of commodity) puts then 120 ℃ of crystallizations 20 minutes.Again Dissolve things inside is moved on in the aluminium dish, wore out 16 hours at 90 ℃.Block at room temperature cools off, and is then that it is levigate.α-maltose content in the powder can be according to described gas Chromatographic Determination of people such as C, C, Sweeley.(seeing U.S. chemical institute magazine, 85 volume 2497-2507 pages or leaves (1963), Journal of the American Chemical Society).According to people such as F.H, Stodola, carry out X-ray diffraction with the Cuk alpha-ray respectively and analyze the gained Icing Sugar, (U.S. chemical institute magazine's 78 volume 2514-2518 pages or leaves, 1956) exist in order to detect crystalline.Used x-ray diffractometer is " GEIGERFLEX RAD-II B ", by Japan, and Tokyo, the Rigaku company of Chiyodaku sells.The result is as the table I.X-ray diffraction spectrum is seen Fig. 1-5.The figure I represents to contain the x-ray diffraction pattern of the unsetting powder of 48% α-maltose, and Fig. 2 is the x-ray diffraction pattern that contains 55.6% preparation crystalline alpha-maltose powder; Fig. 3 is the x-ray diffraction pattern that contains 61.4% preparation crystalline alpha-maltose powder; Fig. 4 is the x-ray diffraction pattern that contains 68.7% preparation crystalline alpha-maltose powder, and Fig. 5 is the x-ray diffraction pattern that contains 74.2% preparation crystalline alpha-maltose powder.
In contrast, get a part " MALTOSF HHH heating for dissolving is in water; vacuum-drying again; levigate; obtain amorphous powder; carry out the X-ray diffraction analysis then, obtain and the similar x-ray diffraction pattern of figure I, " MALTOSE HHH " x-ray diffraction line study collection of illustrative plates see Table 6.
These α-ray diffraction crystallization confirms significantly: α-maltose isomer content that crystallization is required 55% or be higher than 55%, and the maltose content of available maltose raw material is 85% or is higher than 85%.
As shown in Figure 4, the X-ray diffraction analysis has confirmed that the main diffraction angle of preparation crystalline alpha-maltose (2 θ) is 12.6 °, 20.3 ° and 21.9 °.
Experiment 2
Comparison with oil and fat avidity
Experiment 2-1
Hold the comparison of oil capacity
Fresh sample with experiment 1 method preparation is used to measure № 1- 8, and sucrose and lactose are respectively applied for measures № 9 and 10, obtains the particle that size is about 45-150 μ these samples are levigate, then relatively they hold oil capacity.
Holding oil capacity adopts Japanese Patent Application Publication № 31,650/84 described ordinary methods to measure; 10 gram rapeseed oils are placed beaker, mix with Icing Sugar and close stirring.As fructose add not many, mixture has flowability; But along with the sugaring amount increases, mixture is more and more thicker so that be piece.If again sugar is added caked mixture, it will be more and more harder, and at this moment fragmentation holds oil capacity with following formula calculating:
Hold oil capacity=(rapeseed oil (10 gram)/(Icing Sugar (gram)) * 100
It the results are shown in Table II
Experiment 2-2
The comparison of emulsifying capacity
The emulsifying capacity that has compared the various carbohydrate powder of about 45-150 μ median size particulate that make by experiment 2-1 method.
The method of measuring emulsifying capacity is as follows: 2 gram rapeseed oils are placed beaker, add various carbohydrate powder 2 grams, stir with glass stick.The mixture that generates places the test tube with piston to add 30 milliliters in water, and repeatedly the jolting test tube is at room temperature placed and spent the night with mixing, determines the degree of white turbidity by the capacity of visual inspection water layer.
After the microscopic examination water layer, do not see the existence of crystalline powder, but see the oil microdroplets of many about 2-5 μ sizes.Emulsifying capacity is high more, and the number of oily droplet is just many more.
The result is shown in the table II.
These results show that clearly crystalline α-maltose not only has very big oil capacity and the emulsifying capacity of holding, and with oil very large avidity are arranged.
These features help producing the high nutritious prod that food and parenteral contain oil-soluble substance, for example: oil, fat, oil-soluble colorant, oil soluble spices, liposoluble vitamin, fat-soluble hormone etc.
Experiment 3
The comparison of low wash water processed food
The chocolate of application experiment 2 usefulness carbohydrates preparation, as an example of low water content processed food, and in working efficiency, the aspects such as stability of organoleptic property and storage compare.
Chocolate with known method preparation: 40 parts of cocoas are stuck with paste, 10 parts of theobroma oils, and 50 parts of any carbohydrate powder are mixed together, and place refiner.Wear into uniform powder, add 0.5 part of Yelkin TTS, transfer to shell-like container (conche), rub to sneak out at 60 ℃ and make it homodisperse night, after this, mixture places 31 ℃ of insulation cans, before solidifying, theobroma oil injects mould immediately, gas with vibrator eliminating the inside made its curing in 20 minutes by 10 ℃ of cooling ducts, removed mould and packed products obtained therefrom.
In the stage of claying into power, with regard to the difficulty that it runs into, with " excellent ", " poor slightly ", or " poor " represents working efficiency.
Group (10 men and 5 womans) by 15 member compositions finishes sensory test, requires group with " excellent (+1) ", and " medium (0) " and " poor (-) " they are standard, at the component of chocolate, and softening character and the marking of taste aspect.Always assign to judge chocolate quality according to gained.
Relative humidity is to place 4 months at 25 ℃ under 70% condition, detects by an unaided eye and checks chocolate stability.
The result is shown in the table III
These results confirm significantly in chocolate preparation process, crystalline α-maltose is optimum aspect the feature of working efficiency, sensory test and storage stable, no matter it holds oil capacity crystalline alpha-maltose sugar, degree all is applicable to makes high-quality chocolate, thereby be different from the xln beta-maltose hydrate that resembles Japanese Patent Application Publication № 31,650/84.
The X-diffraction investigation that contains the chocolate of crystalline alpha-maltose also shows the diffraction spectra of crystalline alpha-maltose.Thereby this just proves that at the chocolate inner crystalline alpha-maltose that keeps a certain amount of adding they are not subjected to changing as the influence of dissolving or thawing.
Experiment 4
Water content in the high-purity maltose syrup is to the influence of preparation crystalline alpha-maltose
With " maltose HHH " is a kind of Japan, the commodity of the crystalline beta-maltose powder that contains 99.7% maltose that the Hayashibara limited-liability company of Kayama produces.
Part " maltose HHH " is dissolved in a small amount of hot water, places vaporizer, make the syrup of different moisture content through vacuum-evaporation.Add 2% α-maltose seed crystal then, 100 ℃ of following crystallizations 5 minutes, wore out 6 hours down at 70 ℃ again, gained block cool to room temperature is measured its α-maltose isomer content then.
The result represents as the table IV
These result's proofs are in the crystallization of α-maltose, and the suitable water content of high-purity maltose syrup is preferably 2.0%W/W or higher for being lower than 10%W/W, but is lower than 9.5%W/W.
Experiment 5
Temperature is to the influence of preparation crystalline alpha-maltose
With " maltose H studies the influence of temperature to preparation crystalline alpha-maltose, and " maltose H is a kind of Japan, the commodity of the crystalline beta-maltose hydrate that contains 41.5% maltose that the Hayashibara limited-liability company of Okayawa produces.
Get part " maltose H " and be dissolved in a small amount of hot water, put in the vaporizer, obtain having the syrup that water content is 4.5%W/W, add 2% α-maltose seed crystal then through vacuum-evaporation.100 ℃ of crystallizations 5 minutes, pour the aluminum dish into, wore out 16 hours under the differing temps in 20-140 ℃ of scope simultaneously, measure into the content of blocky α-maltose isomers then.
In addition, measure every colour generation degree, by 30%W/W aqueous solution 10cm -1Cuvette be determined at the light absorption ratio of 420nm and 720nm, calculate extinction rate variance (A420-720) then
Its result is shown in the table V
These results confirm preferably 60-120 ℃ of the interior preparation crystalline alpha-maltose optimal temperature of 50-130 ℃ of scope clearly.Simultaneously confirm that also the coloring degree of crystalline alpha-maltose changes with Tc, temperature surpasses 130 ℃ of coloring degrees suddenly to be increased: the degree of staining in the time of 140 ℃ is approximately 14-20 times below 100 ℃; Be approximately 120 ℃ 7 times;
Be 130 3 times.
Experiment 6
Pressure is to the influence of preparation crystalline alpha-maltose
Study the influence of pressure to preparation crystalline alpha-maltose with " maltose HHH ", " maltose HHH " is a kind of crystalline beta-maltose hydrate commodity that contain 99.7% maltose that the Hayasibara limited-liability company of Japanese Okayama produces.
Part " maltose HHH " is dissolved in a small amount of hot water, place vaporizer, boil the syrup that obtains the 5.0%W/W water content in the vacuum, then syrup is placed the pressurized vessel that has agitator, the seed crystal that adds 2% crystalline alpha-maltose, the supply different pressures is 0-20kg/cm under stirring state 2Air 70 ℃ of crystallizations.Spot-check samples contg, measure their α-maltose isomer content then.
The result represents as the table VI
These results clearly prove pressurize, especially at 5kg/cm 2The time, can quicken the crystallization of α-maltose.
Experiment 7
The comparison of package stability
Carry out storage stability test with " maltose HHH ", " maltose HHH " is the commodity that the Hayashibra limited-liability company of a kind of Japanese Okayama produces the crystalline beta-maltose hydrate that contains 99.7% maltose, also be to obtain crystalline α-maltose by the method for testing 1 from " maltose HHH ", the two all is to grind to form tiny particle (powder).
Get every kind of sample 150 gram and place triangular flask, clog with piston then and be placed in 50 ℃ of insulation cans.Serial sampling in the insulating process, the water-soluble one-tenth 30W/W% aqueous solution, and measure its coloring degree and pH.
Use 10cm -1Cuvette is measured the difference (A420-720) of solution light absorption ratio when 420nm and 720nm and is represented coloring degree.
The result is shown in the table VII
Result after comparing under sealed state proves that significantly crystalline alpha-maltose is very stable, is difficult for overstrike and rotten than the crystalline beta-maltose hydrate of commodity.
In addition partial crystallization beta-maltose hydrate and crystalline alpha-maltose is placed in the plate then the stability of its storage of research under 50 ℃ and ambient environmental conditions.Content is not almost seen the browning look or is changed.
We find that crystalline alpha-maltose is better than the crystalline beta-maltose hydrate aspect water-soluble, even also dissolving immediately in cold water.
After the maltose solution of dissolving crystallized α-maltose preparation is by the effect of rough people's kidney alpha-glucosidase, maltose in the solution resolves into glucose rapidly, and this enzyme is according to biochemical magazine Vol 91 PP809-816(1982) (The Journal of Biochemistry) described method preparation.
Under sealing condition, crystalline alpha-maltose is overstrike or change hardly according to description of test; Water-soluble immediately; Solution is very fast to be utilized by a kind of body endoenzyme, and therefore, the origin of heat that crystalline alpha-maltose can be used as intestines and stomach peripheral hyperalimentation product suits.
Several specific embodiment of the present invention will be narrated in the back.
Example A
The production of crystalline alpha-maltose
The liquefaction bacterial of commodity is added in the suspension of a yam starch and 10 parts of water heat and is heated to 90 ℃ and just becomes gelatin-like, be heated to 130 ℃ immediately and end the liquefied starch soln that enzymatic reactions so obtain about 0.5 equivalent glucose (DE).This starch solution is cooled to 55 ℃ immediately, adding is from the starch of the isolated 100 units/gram isoamylases (EC3.2.1.2) of PSeudomonas amyloderamosa ATOC 21262 substratum, it is the commodity of the Nagase limited-liability company production " #1500 " by name of Japanese Osaka, obtains containing the high purity maltose solution of 92.5% maltose in 40 hours in the pH5.0 saccharification.Use activated carbon decolorizing then, again spent ion exchange resin purifying and deionization.Maltose solution is concentrated to 75%, pours crystallizer into, adds the seed crystal of 1 crystalline beta-maltose-hydrate, adjusts to 40 ℃, is cooled to 30 ℃ in two days gradually and can obtains crystallization suspension under mild stirring.From suspension, isolate crystallization with hanging basket type shape whizzer, obtain crystalline high purity beta-maltose hydrate (purity 99.0%) by a small amount of spray washing.
The high purity maltose that obtains is dissolved in a small amount of hot water.Place vaporizer, vacuum-evaporation prepares the syrup that water content is 5.5%W/W.Syrup is put into crystallizer, adds 1% crystalline alpha-maltose seed crystal that the method by experiment 1 test 6 obtains, at 100 ℃ of continuous stirred crystallization 5 minutes, impouring vinyl disc, and 70 ℃ aging 6 hours.Pulverize block product with pulverizer then, dehydrate with thermopnore and obtain Powdered crystalline alpha-maltose that content is 73.3% α-maltose isomers, be approximately 92% with high-purity crystallized beta-maltose hydrate its output that is as the criterion.
Product is a kind of white powder agent of medium sugariness, and product is well suited for being used for food-processing.The low food of water content for example, the food of contg fat-soluble substances, alcoholic beverage etc.; Makeup; Medicine and chemical preparations.
Example A-2
Contain the aqueous solution of the high purity maltose of 92.5% maltose by the preparation of the method for routine A-1, vacuum concentration obtains the solution that water content is 20%W/W.By being installed in the nozzle at spray tower top, the high-pressure pump spraying.Simultaneously 100 ℃ of air blow to a screen conveyor at the bottom of being installed in tower from cat head.It is just carrying crystalline alpha-maltose as the liquefaction of seed crystal and is being collected in powder-product on the screen conveyor, and will generate product at 70 ℃ of air product that liquefaction is come out during 69 minutes during upwards by net place aging tower and wore out 4 hours at 70 ℃ of airflows in tower.Obtaining α-maltose content and be powder crystallization α-maltose of 66.2% is that its output of standard is about 94% with the high purity maltose.
Product is the white powder sweeting agent with medium sugariness, and product is very suitable for the chocolate low as water content of processing food, food such as chewing gum and penuche; Butter butterfat; " an "; " Kyuhi " fish flesh prod; Alcoholic beverage etc.
Example A-3
The liquefy commodity of α-Dian Fenmei of bacterium are added to and are heated to 90 ℃ in the suspension of 2 parts of W-Gums and 10 parts of water and just become gelatin-like, be approximately 2 liquefied starch soln and be heated to 130 ℃ to end enzymatic reaction in order to prepare DE.Starch solution is cooled to 55 ℃ immediately; The starch of the allomerase (EC3.2.1.68) of 120 units/gram that adding makes from Pseudomonas amyloderamosa ATCC 2/262 substratum, the starch that adds the units/gram soya-beta amylase simultaneously, pH.0 saccharification 4 hours, the similar routine A-2 of purification process obtains the high purity maltose solution of 88.6% maltose content, and this solution obtains containing the 3.5%W/W% malt syrup through vacuum concentration.Then syrup is transferred to crystallizer, add 2.5% crystalline alpha-maltose seed crystal that use-case A-2 method obtains, obtain solid after aging 18 hours in the impouring aluminium dish and at 70 ℃ 120 ℃ of crystallizations while stirring 10 minutes.The method of similar routine A-1, solid is standard with the high purity maltose through Powdered crystalline alpha-maltose of pulverizing and dehydration promptly obtains containing α-maltose isomer 63.9%, its output is approximately 94%.
Product is the white powder sweeting agent with medium sugariness.This product is suitable for the chocolate low as water content of processing food, chewing gum, penuche, jam, custard, butter butterfat, " an " very much; Bread product; Kyahi; Fish flesh prod; Alcoholic beverage etc.
Example A-4
45%(W/W) the aqueous solution of " HM-75 ", be that maltose content is that 79.6% Dian Fentang solution is that the product of the Hayashibara limited-liability company of Japanese Okayama is used as material solution, select the i.e. " XT-10ZZE(Na of storng-acid cation exchange resin that the Tokyo chemical industrial company by Tokyo Kita-Ka produces +) " being surrounded by stainless 5.4 centimetres (cm) layer folding post with the aqeous suspension of resin 4 outsides of packing into, the concentration that obtains each post fat bed is 5 meters.(staged) connects the then total resin bed degree of depth of each post is 20 meters.Raw material enters amount in the post for bed volumetrical 5%V/V is 0.13 to separate by each post with 55 ℃ of water with space velocity, keeps the interior temperature of post to collect effluent liquid at 55 ℃ simultaneously.Isolate from effluent liquid and to contain the abundant part of maltose to obtain maltose content be 94.4% high purity maltose solution.Repeat these 20 cycles of operation, concentrate the high purity maltose solution that generates, obtain the syrup that water content is 4.0%W/W behind the vacuum concentration, these syrup are transferred in the crystallization, 2% crystalline alpha that adding makes by routine A-2 method-maltose seed crystal, crystallization is 20 minutes under 110 ℃ of continuous stirrings, makes it to become particle with spiral type extruding granulator.Thing buy property then in kiln, and obtaining crystalline alpha-maltose isomer content in aging 2 hours with 80 ℃ of airflow dehydrations is powder crystallization α-maltose of 69.2%, is standard with the high purity maltose, and its output is 93%.Product is the white powder sweeting agent with medium sugariness, and as the resulting crystalline alpha-maltose of the method for routine A-1, this product is applicable to food-processing, makeup, medicine and chemical preparations etc.
Example B
The production of food
Example B-1 chewing gum
It is crystalline alpha-maltose of 61.4% that 100 portions of chewing gum major ingredients and 380 parts are contained α-maltose amount by the method preparation of experiment 1, glycosyl-sucrose the commodity of the Hayashibara limited-liability company of 1 part of L-aspartoyl-10 parts of " coupling sugar " Japanese Okayama of L-phenylalanine methyl ester, the 15 parts of β that the L-menthol arranged-rings are stuck with paste and a spot of chlorophyll rubs up and sends rivet bucker together to, cut into slices according to a conventional method.
Working efficiency in the manufacturing processed is gratifying.
Product is delicious chewing gum low in calories and has suitable stretching force and satisfied chewing property of mouth.Product can prolonged preservation.
Example B-2
The Bittevsweet(hardship is sweet) chocolate
40 parts of cocoas stick with paste 5 portions of cocoa cream with 55 parts to make α-maltose content by 1 method of experiment be that crystalline alpha-maltose of 68.7% and 0.2 part " α-G-Sweet " rub (mixing) and close, α-G-Sweet is the Tokyo, and Tokyo sugar refines the alpha-glycosyl Stevioside(Steviosides that limited-liability company produces) commodity.Mixture is poured into refiner carefully stir, add 0.3 part of Yelkin TTS, send in the Conche and knead, place insulation can, go into contour forming and be packaged into product.
Working efficiency in the manufacturing processed is gratifying.Can suitably reduce the more expensive cocoa cream and/or the consumption of Yelkin TTS by the amount that increases crystalline alpha-maltose,
Chocolate has fabulous quality structure, solvability, palatable taste and local flavor, and avoid sucrose to cause harm to the people.
Example B-3
Milk-chocolate
22 parts of cocoas are stuck with paste, 15 parts of chocolate creams and 35 parts of α-maltose contents that make by experiment 1 method are crystalline alpha-maltose of 61.4%, 10 parts of cane sugar powders mix, mixture is sent into refiner, carefully is uniformly dispersed with general method, adds 0.5 part of Yelkin TTS and also goes into Conche, in Conche, rub up, put insulation can, go into contour forming, be packaged into product.
Working efficiency in the manufacturing processed is gratifying.
Chocolate has fabulous taste structure and solvability.
Example B-4
Cream paste
1200 parts is crystalline alpha-maltose of 74.2% by α-maltose content of making of experiment 1 method, 1000 parts of oil that make the crisp thin pancake of sponge cake, and 1 part of Yelkin TTS, 1 part of lemon oil and a Rhizoma et radix valerianae oil obtain cream paste with general method mixing.Product is that low sugariness structure and the best good flavored cream of solvability are stuck with paste the best good flavored cream paste of solution.
Example B-5
The cream wafer
The cream paste that makes by routine B-4 method is heated to 40-50 ℃ and is clipped between two wafers.
Product is the high quality cream wafer of a kind of difficult suction and distortion.
Example B-6
Powdery oil
It is to stir simultaneously in crystalline alpha-maltose of 60% promptly to obtain powdery oil by α-maltose of making of experiment 1 method that 80 parts of salad oils (salad) are added to 100 parts.
This product remove to be fit to cooking thick soup, stew, seasoning with mashed potato and mixed fried rice " Cha-ahm(Chinese fried rice that egg and shrimp are arranged) outside also be suitable for being prepared as pancake powder mix, convenient soup blend etc.
Example B-7
Particulate state instant corn thick soup
30 parts of experiment 1 methods make the vegetables oil that α-maltose that content is 61.4% crystalline-maltose and 9 parts of heating dissolve and mix, and add 30 portions of Semen Maydis powder that are gelatin-like, 15 parts of surfaces are the W-Gum of gel, 5 parts of msg powder types, 8 portions of salt, 7 portions of skim-milks and 0.5 part of onion end mix, with a small amount of amylopectin aqueous solution spraying, also go into grain forming device and drying and obtain the title product.
Add hot water dissolve immediately after disperseing simultaneously all delicious corn soup.
Example B-8
Multivitamin
14 parts is crystalline alpha-maltose and 1 part of vitamin A cetylate and 3 parts of W-Gum mixings of 68.7% by α-maltose content of making of experiment 1 method, is transported to tabletting machine.
Every vitamin A Palmiticacid that approximately contains 20,000 international unit (Internotional units).
Vitamin A is difficult for oxidation in the sheet, also flexible type and breaking not quite.
Example B-9
Butter emulsion
80 parts of new fresh hen eggs add 100 portions of powder crystallization α-maltose that make by the method for routine A-1, stir into Mayonnaise-like, add 200 parts of butter while beating, and add a small amount of cognac seasoning when meeting the requirements when reaching.
Product has uniform structure and suitable sugariness to can be used for decorating various cakes.
Example B-10
The cream custard
With 500 parts of W-Gums, 900 portions of powder crystallization α-maltose by routine A-2 method preparation, 9 portions of salt, 1400 parts of new fresh hen egg stirring and evenly mixings add 5000 portions of milk that boiled gradually, stir to become translucent up to the full gel of W-Gum under low baking temperature.Thing cooling to be mixed adds a small amount of vanillin and obtains the cream custard.
Uniform structure that product is glossy is a kind of very tasty food.
Example B-11
" Uiso sweet rice fruit jelly "
With 90 parts of ground rice, 20 parts of W-Gums, 120 portions of powder crystallization α-maltose that make by routine A-4,4 parts of amylopectin (Pullulan), 1 part " matctcha(tea dust) mix, add suitable quantity of water; kneading is placed in the container, steam and made " Matcha-Uire " in 60 minutes.
Product has medium sugariness, and gloss and profile are all very good.
Because the retrograde of starch component is suppressed, but makes the product stable for extended periods of time.
Example B-12
“An”
2000 parts of " nama-an " that make from adzuki broad bean are placed Stainless Steel Kettle, add 900 portions of sucrose and 500 portions of crystalline α-maltose of powder that make by routine A-4 method, stirring heating, the kneading, but avoid burning with non-stick pan at the bottom of to make the title product.
Product structure is fabulous, appetizing " an ".
Example B-13
The lemon fruit jelly
At first 7 parts of agar are dissolved heating in 200 parts of water, dissolve 150 portions of powder crystallization α-maltose that make by routine A-3 method again, mixture is cooled to 65 ℃ adds 350 parts of water that are filled with carbonic anhydride that contain a small amount of lemon flavour and tinting material, injection mould moulding and cooling obtain product.
Product is the good delicious lemon fruit jelly of a kind of structure.
Example B-14
Sweet condensed milk
In 100 parts through 80 ℃ of 10 minutes disinfectant milk in, add 16 portions of powder crystallization α-maltose that obtain by routine A-2 method at 50 ℃ of vacuum concentration.Reach till 1,305 up to the density of mixture during at 50 ℃.
Product is a kind of sweetened condensed milk that medium sugariness and high stability are arranged.
Example B-15
Jam
1500 parts of fresh grass are mould, 640 portions of sucrose, 640 portions of powder crystallization α-maltose that make by routine A-1 method, 5 parts of pectin, 1 part of citric acid, heating concentrates and obtains the title product in pot.
Product has suitable gel-strength, and suitable sour-sweet taste.
Example B-16
Hard candy
The glycosyl sucrose syrup commodity that the Hayashibara limited-liability company that 100 parts " Coupling Sugar " is a Japanese Okayama produces, add 20 portions of powder crystallization α-maltose that make by routine A-2 method, heating for dissolving, endure water content and be lower than 1.5%W/W, can obtain the colourless boiled sweet of gratifying transparency with the general method casting.
This product has medium sugariness but is not sticking.
Example B-17
The synthetic alcohol beverage
With powder crystallization α-maltose that 40.0 grams obtain by routine A-2 method, 1.1 gram Sodium Glutamates, 7.2 gram citric acids, 1.4 the 75%W/W lactic acid of gram, 0.6 gram potassium primary phosphate, 0.6 gram SODIUM PHOSPHATE, MONOBASIC, 0.6 the gram calcium monohydrogenphosphate, 1.2 gram sodium succinates, 1.1 gram salt, 0.4 gram L-Ala, 0.3 adding water to cumulative volume again after gram glycine, 4ml fluid flavoring etc. are dissolved in and mix in 3.9 liters of alcohol that concentration is 35%V/V is 10 liters, separates then, filtration sterilization, bottling promptly gets above-mentioned title product.
Because crystalline alpha-maltose can be dissolved in 35%V/V alcohol immediately, so working efficiency is gratifying.
Product is suitable " synthetic alcohol beverage.
Example B-18
The fresh Radix Raphani pickles of Bettara-Zuke()
4 portions of powder crystallization α-maltose that obtain by routine A-3 method, 0.05 part licorice extract, 0.08 part oxysuccinic acid, 0.07 part Sodium Glutamate, 0.03 part of Sorbic Acid sylvite and 0.2 part of amylopectin (Pullulan) mix equably and obtain " mixture in early stage of battoro-zuke-no-moto(bettara-zuke).30 kilograms of fresh Radix Raphanies are at first pickled with sucrose with salt according to a conventional method then.Further use the pickled title product that promptly obtains in the seasoning soln that 4 kilograms " battoro-zuka-na-moto " make.
This product has the property of salting down sugariness moderate, and color and luster is good, tastes good.
Example C
Convenient parenteral high nutritious prod
Example C-1
Injection
50 grams are installed in the 600ml vial soft rubber ball beyond the Great Wall respectively by the no thermal source crystalline alpha-maltose of routine A-1 method preparation under aseptic condition, seal and obtain making things convenient for stomach peripheral hyperalimentation injection.
This injection is still stable through prolonged preservation, though at room temperature also like this, thus needn't cryopreservation, the water-soluble of injection is gratifying.
Can be with suitable injection system such as intravenous drip with injection in the 500ml sterile distilled water dissolving bottle.
Example C-2
Hemodialysis
500 grams are made apyrogenic crystalline alpha-maltose by routine A-2 method, and what tinning obtained being used for hemodialysis makes things convenient for stomach peripheral hyperalimentation product.
The same with the product of routine C-1, this kind makes things convenient for stomach peripheral hyperalimentation product that gratifying stability and solvability are arranged.
A kind of aqueous solution preparation of the hemodialysis of producing when " Kindoly SOLN-GF " Pharmacy stock Co., Ltd of Toyota, when using preceding 30 times of sterile distilled waters dilution, preparation dissolves the final concn that makes maltose with liquid preparation and reaches about 0.5%W/W.The solution that obtains like this is effective to insulinopenic patient such as diabetics's hemodialysis.
Example C-3
Injection
Use according to routine A-4 method to obtain, no thermal source crystalline alpha-maltose of 1,985 part adds 0.01 part VitB1,0.05 the 2 gram mixtures that part calcium chloride makes place the 30ml vial, beyond the Great Wall soft rubber ball, seal and get, make things convenient for the injection of parenteral nutrition.
As routine C-1 product, this injection has gratifying stability and solvability.
In bottle, take in as intravenous injection with suitable mode with 25ml stroke-physiological saline solution dissolving injection.
Example C-4
Injection
With 4.96 portions that make by routine A-1 method no thermal source crystalline alpha-maltose, the 5 gram mixtures that 0.03 part of soybean oil and 0.01 part of vitamin-E acetic acid are made place the 60ml vial, charge into nitrogen soft rubber ball beyond the Great Wall, seal and obtain making things convenient for the closed type injection.
The same this injection with routine C-1 product is stablized fabulous solubleness and emulsifying property simultaneously.
Dissolve injection with the 50ml sterile distilled water in bottle, the appropriate injection mode is taken in and is peritoneal injection, also is suitable for intubate and feeds and to raise.
Example C-5
Intubate is fed and is raised
Obtain 20 portions of crystalline alpha-maltose with method, 0.18 part of Sodium Glutamate of 1.1 parts of glycine, 1.2 portions of salt by routine A-3,1 part of Trisodium Citrate, 0.1 part of magnesiumcarbonate of 0.4 part of calcium lactate, 0.01 part of VitB1,0.01 the 24 gram mixtures that part riboflavin is made place aluminium foil, add heat-sealing aluminium bag then.
The same with the product of routine C-1, this preparation stabilization also has fabulous water-soluble.
During use, add about 300-500 ml water in one bag of preparation, raise or intestines are raised with intubate nasal feeding stomach.
Said preparation solution is applicable to that as the high nutritious prod of parenteral the people also is applicable to domestic animal.
Example C-6
Intubate is fed and is raised
With 580 portions of crystalline alpha-maltose by routine A-4 method gained, 195 parts of dehydration yolk, 209 portions of skim-milks, 4.4 parts of sodium-chlor, 1.85 part Repone K, 4 parts of sal epsom, 0.01 part of VitB1,0.1 part of SODIUM ASCORBATE, 0.6 part vitamin-E acetate, 0.04 the 25 gram mixtures that part nicotinamide is made place aluminium foil bag, the heated sealant aluminium foil bag.
The same with the product of routine C-1, this preparation stabilization also has fabulous solvability and dispersed one bag of preparation approximately to add the 150-300ml water dissolution, and intubate is fed and raised mode such as nasal feeding, esophagus or stomach are raised then.
Example C-7
Intubate is fed and is raised
With 16.5 portions of crystalline alpha-maltose that obtain by routine A-1 method, add 4.05 portions of sucrose, 3.2 the powder juice of a part unshu-mikan(red tangerine, 0.11 part citric acid, 0.02 part xitix, 0.1 portion powder orange juice and 0.02 part of amylopectin make 400 gram mixtures, packing into has in the jar of screw cap, promptly makes one and makes things convenient for stomach peripheral hyperalimentation product.
The same with routine C-1 product, this preparation stabilization, solvability is fabulous.
About 25 restrain agent with the big dissolving of about 100-150ml, feed by intubate nasal feeding or oesophagus then and raise.
The table I
Mensuration maltose raw material maltose content (%) α-maltose isomer X-ray diffraction
(trade name) content (%) crystal diffraction spectrum
1 MALSTAR (R)68.4 48.0 no Fig. 1
2 HM-75,79.6 48.0 no Fig. 1
3 SUNMALT (R)85.8 55.6 have Fig. 2
4 MALTOSEH 91.5 61.4 have Fig. 3
5 MALTOSEHH 96.2 68.7 have Fig. 4
6 MALTOSEHHH 99.7 74.2 have Fig. 5
7 MALTOSEHHH, 99.7 48.0 no Fig. 1
8 MALTOSEHH 99.8 2.3 have Fig. 6
The table II
The experiment preparation crystalline alpha-maltose is held the oil capacity emulsifying capacity
Content (%)
1 48.0 nothings 45-
2 48.0 nothings 49-
3 55.6 have 110 ++ ++
4 61.4 have 126 ++ +++
5 68.7 have 95 ++ +++
6 74.2 have 7.3 ++ +++
7 48.0 nothings 47-
8 2.3 have 53 ++
9-have 36+
10-have 40+
The table III
α-maltose same feeling functionary-enterprise is commented as integral body
Test number divides isomer crystalline rate stabilised efficiency sexual valence
Content (%)
1 48.0 indifferences+7 make moist, softening contrast
The fatty frosting of part
2 48.0 indifferences+10 make moist and soften contrast
The fatty frosting of part
3 55.6 have excellent+42 no change the present invention
4 61.4 have excellent+45 no change the present invention
5 68.7 have excellent+45 no change the present invention
6 74.2 have excellent+45 no change the present invention
7 48.0 indifferences+8 make moist and soften contrast
The fatty frosting of part
8 2.3 have poor slightly+24 parts sugar frosting contrast
9-there is excellent+26 parts sugar frosting to contrast
10-there are poor slightly-41 fat and sugar frostings to contrast
The table IV
Water content crystalline alpha-maltose in the syrup is commented on differentiation
(W/W%) structure body burden (%)
2.1 57.2 the present invention are arranged
3.5 73.8 the present invention are arranged
5.0 74.2 the present invention are arranged
7.1 70.1 the present invention are arranged
8.6 66.3 the present invention are arranged
9.3 59.4 the present invention are arranged
12.3 have *25.2 the present invention
15.0 have *33.8 contrast
Annotate: * refers to have crystalline beta-maltose to occur
The table V
Temperature crystalline alpha-maltose is estimated with differentiation A 420-720
(℃) content (%) of structure body
20 have 50.4 0.17 contrasts
40 have 51.6 0.16 contrasts
50 have 56.3 0.16 the present invention
60 have 62.9 0.15 the present invention
70 have 64.1 0.17 the present invention
80 have 65.4 0.18 the present invention
100 have 62.8 0.21 the present invention
120 have 59.1 0.43 the present invention
130 have 56.8 0.86 the present invention
140 have 53.3 2.98 contrasts
The table VI
The same differentiation of crystallization pressure crystalline alpha-maltose
(kg/cm 2) structure thing content (%)
1 has 58.4
1 has 61.6
2 have 63.8
5 have 65.3
10 have 65.4
The table VII
Store all samples
Phase (week) crystalline beta-maltose hydrate crystalline alpha-maltose
0 degree of staining 0.056 0.094
pH 4.30 4.35
2 degree of stainings 0.145 0.096
pH 3.56 4.40
4 degree of stainings 0.236 0.096
pH 2.92 4.40
6 degree of stainings 0.310 0.096
pH 2.87 4.40
10 degree of stainings 0.408 0.096
pH 2.83 4.40

Claims (11)

1, the method for preparing preparation crystalline alpha-maltose, this method comprises:
Use based on the dry solids wt meter from containing 85% or be higher than 85% high purity maltose and prepare the high-density syrup that water content is lower than 10% (W/W);
50-130 ℃ of scope, α-when the maltose crystal seed exists, go out α-maltose by above-mentioned syrup crystallization is arranged; With
Reclaim the preparation crystalline alpha-maltose that contains 55% (W/W is based on the dry solids wt meter) α-maltose isomer at least.
2, method according to claim 1, wherein the water content of indication high-density syrup is at 2.0-9.5%(W/W) scope.
3, according to the described method of claim 1, wherein crystallisation step carries out under promotion crystalline high pressure.
4, method according to claim 1, its mesohigh is up to about 20kg/cm 2
5, according to the described method of claim 1, crystallisation step wherein carries out under dehydration conditions.
6,, it is characterized in that wherein crystallisation step comprises crystallization and aging two steps according to the described method of claim 1.
7, according to the described method of claim 1, wherein indication α-maltose is the divided powder shape.
8, according to the described method of claim 1, wherein the colourity of indication preparation crystalline alpha-maltose is less than 1.0.
9, according to the described method of claim 1, wherein the high-purity maltose of indication is by carrying out starch saccharification with beta-amylase or beta-amylase and a kind of starch-debranching enzyme, and hydrolysate is purified to be obtained.
10, according to the described method of claim 1, wherein the indication high purity maltose is to separate a kind of sugar soln by the salinity level with storng-acid cation exchange resin, reclaims to be rich in the maltose part and to obtain again.
11, according to the described method of claim 1, wherein the indication preparation crystalline alpha-maltose is 12.6 ° in the main diffraction angle (2 θ) of carrying out with the Cuk alpha-ray showing when X-ray diffraction is analyzed, 20.3 ° and 21.9 °.
CN85105158A 1985-04-11 1985-07-06 Process for preparing alpha-maltose crystals Expired CN1013336B (en)

Applications Claiming Priority (2)

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JP77029/1985 1985-04-11
JP60077029A JPS617214A (en) 1985-04-11 1985-04-11 Solid preparation for parenteral nutrition supply to be dissolved on use

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