CN1034578C - Modified starch emulsifier characterized by shelf stability - Google Patents
Modified starch emulsifier characterized by shelf stability Download PDFInfo
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- CN1034578C CN1034578C CN89105576A CN89105576A CN1034578C CN 1034578 C CN1034578 C CN 1034578C CN 89105576 A CN89105576 A CN 89105576A CN 89105576 A CN89105576 A CN 89105576A CN 1034578 C CN1034578 C CN 1034578C
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Abstract
Modified starches useful for emulsifying industrial products, especially foods and beverages containing flavor oils, are prepared by enzymatic degradation of the 1,4-alpha-D-glucosidic linkages from the non-reducing ends of a starch molecule, preferably employing beta-amylase, which may be carried out before or after the preparation of a starch derivative containing a hydrophobic group or both hydrophilic and hydrophobic substituent groups. The enzymatic degradation provides a starch emulsifier whose emulsions are characterized by improved shelf stability, which emulsifier may be used as a replacement for gum arabic and in other industrial applications.
Description
The present invention relates to a kind of treated starch, this treated starch can be used in the emulsion of anti-storage, and can in the stable oil-in-water emulsion system of need, be used as the surrogate of Sudan Gum-arabic, particularly be used in the beverage with the flavouring agent oil blending of citrus oil and so on.The invention still further relates to a kind of method of this treated starch of preparation and chemical composition, the food and drink that contain this treated starch.
Many Chemical Composition can be used as emulsifying agent in industry such as food, makeup, paint, medicine and polymkeric substance and in textiles processing, leather processing, ore floatation, petroleum drilling and agricultural spray operation.In these many application, emulsifying agent also plays the function of the flowability of viscosity stabilizer or external phase simultaneously.Usually, in using, these require this emulsion that the shelf stabilities of long period is arranged.
The typical composition that can play water soluble emulsifier and stablizer function includes guar gum, Sudan Gum-arabic and other glue classes, starch, protein, various water-soluble polymerss etc.(Encyclopedia of ChemicalTechnology Kirk-othmer compiles, the third edition, Wiley-Intersci-ence New York referring to " encyclopedia of chemical technology ", 1979, the 8th volume 900-910 page or leaf, 918 pages, 923-925 page or leaf and the 12nd volume 55-56 page or leaf).Sudan Gum-arabic is because its shelf stabilities is preferred in many application, particularly in the refrigeration or freezing storage of emulsion.
Sudan Gum-arabic is a kind of replacement mixed polysaccharide of side chain, it is characterized by water-soluble greatly, viscosity is low, and do not have smell, colourless, tasteless.Sudan Gum-arabic is in food such as candy, syrup, local flavor oil-emulsion, ice-creams and beverage and be used as emulsifying agent or stablizer in ink, tackiness agent, textiles and the printed liquid.
Sudan Gum-arabic is a kind of natural gum that grows in the Middle East and Africa.Because Sudan Gum-arabic derives from these areas, thus very expensive, and it is supplied and quality also can't be scheduled to.Therefore industry member is being sought a kind of shelf-stable always for a long time, cheap Sudan Gum-arabic surrogate, and found that the starch derived product can be used for this order ground.
United States Patent (USP) such as (Caldwell people) of announcing December 1 nineteen fifty-three discloses the dicarboxylic anhydride starch half ester derivatives that replaces for 2,661, No. 349.In these derivatives, have some can form stable oil-in-water emulsion, it is applicable in the application of beverage emulsion, flavour substances emulsion and other emulsion.Consult chapter 9 in " treated starch: character and purposes " book (P.Trubianu, Chapter 9, in ModifiedStarches:Properties and uses, CRC press, BocaRaton, Florida, 1986, P.134-147).Cold-water-soluble, low viscous octene succinate starch derivative has successfully replaced Sudan Gum-arabic in carbonated drink.The octene succinate derivative of viscosity higher in salad dressing as the surrogate of Sudan Gum-arabic.The dicarboxylic acid starch half ester derivatives of these replacements has also replaced Sudan Gum-arabic to be used for the capsular hydrophobic substance of outsourcing, for example local flavor material, VITAMIN, spices and wet goods.Typical outsourcing capsule is by a kind of oil-in-water emulsion preparation of spraying drying.Some capsule medium has been modified into a kind of composition, and it can little by little discharge or controlledly discharge the flavour substances or the oil of embedding.There are some can in water, dissolve in addition, may more be better than Sudan Gum-arabic in some applications than the more solid substance of its corresponding Sudan Gum-arabic.
Low viscosity (conversion) starch that is used for beverage and flavour substances emulsion normally acid degradation by starch prepares.The production method of low-viscosity starch is known.(Richards's etc.) United States Patent (USP) of announcing on July 12nd, 1977 discloses a kind of degradation method of oleophylic substituted starch for 4,035, No. 235, and it is to digest with α-Dian Fenmei to replace acid degradation and prepare low-viscosity starch.This oleophylic substituted starch is applicable to that the capsule of flavour substances seals and oil-in-water emulsion.The starchbased product that these method for transformation make is applicable to as drink and has been degraded into maltose, has perhaps reached desired terminal point (be the existing enough degrees of degradation of this starch, the extraordinary emulsion for preparing with this starch has improved shelf stabilities).This terminal point can be used viscosity change, the content of reducing sugar, or any other measurement starch molecule enzymolysis degree methods known in the art is measured.Another kind method is to allow enzymolysis proceed, till all effectively the maltose unit has all broken away from starch molecule basically.Degradation time becomes with concentration and other variable factor of temperature, enzyme and substrate, is generally several hours to 24 hours or the longer time.With heating, adding chemical substance or other deactivating enzymes known in the art or with the isolating method of enzyme-to-substrate enzyme liberating is stopped then.
Formed degraded starch composition can reclaim with spraying drying, roller drying or other form that is suitable for using.
Should be understood that to the present invention includes any emulsive composition that emulsifying agent wherein is the starch that has improved the emulsion shelf stabilities through the enzyme process improvement.Therefore, it means the emulsion that comprises the mixture that contains treated starch and natural gum or other emulsifying agents.
Treated starch of the present invention can advantageously be applied to any with in the product of Sudan Gum-arabic as emulsifying agent, stablizer etc., and be applied to that any need form with the high-molecular weight water soluble emulsifier or the product of stabilized emulsion in.Therefore, it can be applicable to the beverage with mandarin oil or lemon oil seasoning, various confectionery, ice-creams, and other requirement has in the drink and food of shelf stabilities emulsifying agent.It can be applicable in water-based beverage and the pure base beverage.This starch also can be used for preparing the purposes of spray-dired local flavor oil (can form flavor emulsion after this oil rehydration), ink, textiles and other non-food products.
The available starches that can be used for preparing enzymolysis starch of the present invention derives from any plant material that comprises corn, potato, sweet potato, wheat, rice, western paddy rice, cassava, glutinous corn, Chinese sorghum etc.Also comprise the conversion product that from above-mentioned any starch, obtains, for example, by the fluidity starch or the thin boiling starch of method preparations such as oxidation, α-Dian Fenmei conversion, weak acid hydrolysis or heating dextrinization, and the derivatized starch of etherificate and esterification.
Preferably a kind of pasted starch of this starch (a kind of on-granulated starch of par-boiled) also can be a kind of through the fluidity starch weak acid degraded or that heating dextrinization method transforms, and the technology of described method for transformation is all known." starch and modification thereof " (Starch and Its Modifications) referring to M.W.Ruten berg, " water-soluble gum and resin handbook (Hand book of Water-Soluble Gums and Resins), R.L.Davidson, editor, HcGraw Hill, Inc.New York, 1980, the 22-36 page or leaf).These transformation technologies can single use or several being used in combination.This transformation is carried out before handling with hydrophobic/hydrophilic reagent (or only using hydrophobic agents) and before handling with beta-amylase.When needing, also available α-Dian Fenmei handles converted starch, to produce disclosed fluidity starch in a kind of picture United States Patent (USP) 4,035,235.The conversion of α-Dian Fenmei was generally carried out before beta-amylase is handled.When the full-bodied emulsifying system of needs, just need not converted starch.
Starch can be derived with any agent treated that makes starch have emulsifying property.Derivatization can be carried out before or after beta-amylase is handled.Described reagent must contain a hydrophobic portion separately can contain a hydrophilic segment.Hydrophobic part should be alkyl, alkenyl aralkyl or aralkenyl, and these groups contain 5 carbon atoms at least, preferably 5 to 24 carbon atoms.Propose in the preferred version that can be as described below like that, provide hydrophilic segment by reagent, perhaps as in further embodiments, as hydrophilic segment, and reagent only provides hydrophobic part with the hydroxyl of starch self.
In a preferred version, deriving of starch is method with described in No. 2,661,349, the United States Patent (USP), promptly undertaken by reacting with an alkene basic ring dicarboxylic anhydride.But any method that is used for derivatized starch makes starch molecule produce required hydrophobic and hydrophilic dual-use function, thereby makes starch have stable emulsifying property, may be used to prepare the treated starch of requirement of the present invention, comprises also ignorant method in this area.
When needs low viscosity emulsifying agent, preferred scheme is an octene succinic acid starch half ester derivatives that contains amylopectin, glutinous corn for example, and its current degree (WF) has been converted to about 60.The current degree is to record in the viscosity empirical experiment that a scale is 0-90, and mobility wherein is the inverse of viscosity.The typical measuring method of starch current degree is with the rotary shear-type viscometer of a kind of Thomas (Thomas Rotational Shear-TypeViscometer, make by U.S. Arthnr H.Thomas company, Philadelphia, PA19106), this viscometer is that the standard oil of 24.73 centipoises is demarcated at 30 ℃ with a kind of viscosity, and this oil requires 100 rotations to need 23.12 ± 0.05 seconds.Obtain accurately and reproducible current degree by measure time that per 100 rotations are consumed under different solid content, different solid content is (along with transforming degree increases, viscosity degradation) of being decided by the transforming degree of starch.In a preferred examples, use 0.25% at least, be preferably the starch that 3.0% octene succinyl oxide is handled conversion.When needing, also can use a kind of hydroxypropyl octene succinate derivative.
For other products, can adopt any replacement degree or level of conversion to produce desired viscosity and emulsification property.For example, United States Patent (USP) 4,035 discloses a suitable scheme No. 235, it comprises the method for the hydrophilic derivant that is used for producing a kind of starch, this derivative when sealing water-fast material such as volatile flavor oil or spices as the surrogate of Sudan Gum-arabic.
In a preferred embodiment, second step after the preparation starch derivative is this deutero-starch of gelatinization.Gelatinization process makes starch molecule launch from grainy texture, thereby makes the enzyme can be more easily and the outside side chain of degraded starch molecule.After the starch slurry gelatinization, the slurry solid substance, temperature and pH regulator to can provide the best enzymic activity.
The optimum parameter of enzymic activity will be different and different with used enzyme.Therefore, the speed of enzyme liberating is different with various factors, and these factors comprise whether used enzyme type, enzyme concn, concentration of substrate, pH, temperature, inhibitor exist and other factors etc.According to enzyme type or its source, may need to adjust parameters to obtain best digestion rate.Usually, preferred enzymic digestion reaction is to carry out under the highest solid content, and the drying of starch composites after this helps can keep best speed of reaction simultaneously again.For example, for use in the beverage for the emulsifying agent of barley beta-amylase production, the precooked starch dispersion system reaches at 33% o'clock for best in solid content.Also can use higher solid content, still, higher solid content can cause stir difficulty or effect bad, also more difficult to the operation of starch dispersions system.
Though method of the present invention adopts beta-amylase to illustrate as enzyme component, other enzyme also can be used for preparing treated starch of the present invention, for example, outer-α-1.4-Polyglucosidase, outer-1,4-α-D-dextran Fructus Hordei Germinatus tetrahydrochysene lytic enzyme, outward-1,4-α-D-dextran Fructus Hordei Germinatus six hydrogen lytic enzymes, or any other can be optionally disconnects 1 from the non-reducing end of starch molecule, the 4-key still can not disconnect 1, the exoenzyme of 6-key.
Because these exoenzymes can only be removed glucose, maltose or bigger sugar unit from the outside side chain of amylopectin molecule, and can not make molecule slough side chain, so this enzyme liberating process produces the molecule that its short chain tapping point is kept perfectly.In amylopectin, tapping point accounts for the 4-5% of the monosaccharide unit of molecule.Along with the enzymolysis of amylopectin, the outside side chain of molecule is shortened, up to the association with other side chains reduces or eliminates that, those that stay 1,6 tapping point has stoped the association of inner side chain.So the molecule of degraded demonstrates the improved anti-effect of bringing back to life storing and freeze/melt in the circulation.Just because of this reason, can only disconnect 1,4 key and the exoenzyme that can not disconnect 1,6 key is the key element of necessity of the present invention from the non-reducing end of starch molecule.
Though used the enzyme in the solution in the method for the present invention, utilized the method that is fixed on the enzyme on the solid carrier also to be applicable to the present invention.
The optimum concn of enzyme and substrate is by the flat decision of enzyme running water.Enzymic activity can be represented with the saccharogenic power number of degrees (DP °) of every milliliter of enzyme aqueous solution.DP ° is the enzyme amount in being contained in 0.1 milliliter 5% sample enzymes soln, when this sample with 100 milliliters of substrates 20 ℃ of insulations in the time of a hour down, described enzyme amount can produce enough reducing sugars and reduce 5 milliliters of fehling's solutions.This method of measuring DP ° see " food chemistry product standard " (Food ChemicnlsCodex third edition Nafional Acndemy Press Washing tonD.C.1981, P.484).
Under optimum temps and pH condition,, need to contain the gelatinization of starch solution of 33% solid substance so that in 8 hours, degrade above 334DP ° with dry weight basis 100 gram starch.With dry weight basis 100 gram starch (pH is 5.3, and temperature is 57 ℃), DP ° is worth preferably 840-1110.
Reaction can be carried out in the presence of buffered soln, to guarantee that in whole degradation process it is best that the pH value keeps.Damping fluid can be used acetate, Citrate trianion or other faintly acid salt.Can also utilize other reagent to obtain best enzymic activity.Reaction can be carried out between 55～60 ℃ of pH3～10, and preferred pH is 5～7, and best pH is 5.7.
In the enzymic digestion process, the temperature of the aqueous dispersion of starch should remain on 20～100 ℃, and preferred temperature is 55～60 ℃, and optimum temps is 57 ℃.But if require the short reaction times, then temperature can perhaps be used higher enzyme concn between 60～63 ℃.As for other parameters in the enzyme reaction, preferably the temperature range with the best will change with the variation of other parameters, and these parameters comprise concentration of substrate, pH and influence other factors of enzymic activity that these can be decided by the practitioner.
Enzyme reaction can continue to and reach desired palliating degradation degree, perhaps proceeds to all can utilize maltose to go up all substantially to remove from starch molecule.The process of the enzyme reaction mensuration that can in all sorts of ways.If it is all definite to obtain all key parameters of a certain specific starch composites, then can allow reaction proceed to predetermined relative end time (promptly as 8 hours among the embodiment 1).This terminal point also can be controlled and limit by the concentration of measuring reducing sugar.By 1, the maltose that 4-α-D-glucosidase activity produces is a kind of reducing sugar, and it can be quantitative with method well known in the art.Other technologies are for example controlled viscosity change or change of molecular weight, also can be used for the terminal point of defined reaction.
In a preferred embodiment, be contained in the recently definite degraded terminal point of percentage of the reducing sugar in the reaction medium by measurement.Each maltose unit contains two glucose units, but has only a reduction group to be measured in reducing sugar analysis.So the weight percent of reducing sugar (calculating with glucose) almost equals half of the unitary weight percent of maltose that formed by the starch molecule degraded.If pollute in the beta-amylase a large amount of α-Dian Fenmei is arranged, then may contain more reduction group in the reaction medium, consider that these pollutents to measuring the influence of enzyme reaction process, must make it stdn when measuring reducing sugar.Another kind of way is to utilize other analytical procedures known in the art directly to measure maltose.
Can change for the needed starch degradation degree of low-temperature stability of improving the starch composition.It depends on the type of used starch, substituent existence and character, and if replacement, the degree of conversion arranged.Known starch can improve the low-temperature stability (seeing United States Patent (USP) 3,525, No. 672) of thickening material when degraded 13～55% (by weight).For the purposes of low viscosity emulsifying effect (be starch be transformed into the current degree be 40～60), the starch that degradation process must proceed to 70% (weight) has been hydrolyzed into till the maltose, and this is to determine by the reducing sugar content of measuring in the starch dispersions system.
Theoretically, utilizing pure beta-amylase and unconverted starch to carry out enzymolysis, is that the maximum of maltose can reach about 55% of starch weight with starch degradation.But there is not pure commodity beta-amylase.The commodity beta-amylase contains a spot of α-Dian Fenmei, and α-Dian Fenmei is a kind of endoenzyme, and it is the starch side chain of breaking inner arbitrarily, and the side chain of disconnection is worked with beta-amylase.With acid, heating or oxidation starch is transformed, but remarkable to the effect of starch not as beta-amylase.Therefore, use pollution to have the beta-amylase of a small amount of α-Dian Fenmei can make the degraded of starch reach 70% (weight).
After reaching desired starch degradation degree, can be with enzymatic inactivation.Beta-amylase is passivated under about 100 ℃ temperature very soon, therefore, by the temperature of starch dispersions system is elevated at least 75 ℃, at least 15 minutes time, can make reaction terminating easily.
The practitioner will find that the order of step in the inventive method can carry out with any order, and is not limited to the order in the above-mentioned preferred embodiment.Therefore, in second embodiment preferred, reversed in order, enzymolysis step are to finish before the derivatization step.
If final application purpose requires starch component is purified, then maltose and other reaction impurities and byproduct can by dialysis, filtration, centrifugal or any other known in the artly be used to emanate and the technology of concentrated starch component is removed.
If final application purpose requires the exsiccant starch component, then can make the starch component dehydration with any technique known in the art.
In the defective material flavor emulsion was used, the most handy current degree that changes into was about 40～60 viscous maize starch.
Concerning the low viscosity emulsifying agent, can measure degraded with the reduction of enzyme reaction medium viscosity and whether meet the requirements of degree.In embodiment 1, set forth a kind of method of control reaction soln viscosity.Can adopt any method in known many viscometric methods.But, except desired enzymic activity, also have many factors that viscosity is changed.For example, if contain a large amount of α-Dian Fenmei in the beta-amylase, then just there is not direct correlationship between the reduction of viscosity and the beta-amylase activity.So, if measure the degree of enzyme liberating with viscosity change, then must careful monitoring and the degree polluted of control α-Dian Fenmei.If 1 of used here beta-amylase or any other, 4-α-D-Polyglucosidase contains a large amount of α-Dian Fenmei pollutents, and then beta-amylase before use should first purifying, perhaps adds alpha-amylase inhibitor in the reaction dispersion liquid.
Following examples will be illustrated the present invention more fully.In these embodiments, except as otherwise noted, otherwise part of mentioning or per-cent all are with dry weight basis, and temperature all is degree centigrade.Shelf stabilities is measured quickening at low temperature and is brought back to life and shorten the test period.
Embodiment 1
Present embodiment has been set forth the preparation method of a kind of treated starch of the emulsifying effect that the present invention is used for the drink flavour material.
Utilize United States Patent (USP) 2,661, disclosed method has prepared a kind of octenyl succinate derivative (OSA) in No. 349 example II from viscous maize starch, different just replaced W-Gum with glutinous corn.In addition, with the same starch reaction of 3% octenyl succinic acid anhydride, rather than picture is in the publication used 0.5%.One 28% glutinous corn OSA slurries are jet cooking under about 149 ℃ (300 °F).To boil complete glutinous corn OSA then and be placed in 55～60 ℃ of waters bath with thermostatic control, be stirred simultaneously.Hydrochloric acid with 3% is transferred to 5.3 with pH.
Be divided into four parts boiling complete glutinous corn OSA dispersion liquid, add the barley beta-amylase (1,4-α-D-dextran maltose lytic enzyme) of different amounts in each part, this barley beta-amylase is available from Fermco Biochemicals, lnc, ELK GroveVillage, Illinois).The enzyme amount that adds is respectively 168,334,840 and 1110 DP °/100g glutinous corn OSA dry weight.This scope that has recorded enzyme concn in the experiment in front can produce desired starch degradation degree in about 8 hours.Per 100 gram starch contain at least, and those three batches of starch of 334DP ° have all reached desired palliating degradation degree in 3-8 hour.
Palliating degradation degree is measured with control dispersion liquid " funnel " viscosity (funnel Viscosity).Correspondingly, should control the α-Dian Fenmei pollution level that exists in the barley beta-amylase, be restricted to every milliliter of enzyme solution and be no more than 0.4 dextrinization unit (DU), can make viscosity not be subjected to the influence of this variable like this.A dextrinization unit is meant having in the presence of the excessive beta-amylase, in the quantity of α-Dian Fenmei of 20 ℃ of energy during with the speed gelatinization Zulkovsky starch of 1 gram per hour.
For measuring " funnel " viscosity, taking by weighing 38 gram modified starches (analyse to do and calculate) in 250 ml beakers (stainless steel) that tared, has a thermometer in the beaker, and adding distilled water is 200 grams to gross weight.Sample is mixed dissolving all agglomerates, and heating or be cooled to 22 ℃ (72).The starch dispersion liquid that boiled is added to one is with in the graduated graduated cylinder, measure 100 milliliters.Pour into then in the funnel of calibrating, seal aperture with finger simultaneously.Allow paucidisperse liquid flow back to the air that graduated cylinder sandwiches with removal, the dispersion liquid that will stay in the graduated cylinder is refunded funnel again.Write down these 100 milliliters of sample stream with a timing register and spend the terminal required time of funnel.
This funnel is 58 °, a heavy wall of a standard, and resistance glass funnel, top diameter are 9～10 centimetres, and the inside diameter of the thin neck of funnel is about 0.381 centimetre.Funnel is calibrated with above-mentioned side's method, makes 100 ml waters to pass through for 6 seconds.
Parameter and restriction α-Dian Fenmei by the test of careful control funnel viscosity are polluted, and beta-amylase is made between the loss of degree with viscosity of starch degradation have dependency.Decide reducing sugar to determine the degree of degraded with Fehling method paste.
In the present embodiment, desired enzyme reaction terminal point reaches between 9～50 seconds in funnel viscosity.The reducing sugar content of these samples is between 29～35%.Corresponding starch degradation by weight is 58～70%.When viscosity reaches standard, in reaction soln, feed open steam, reach at least 75 ℃ up to temperature, and kept this temperature at least 15 minutes, so that enzymatic inactivation.Then with each batch dispersion liquid spraying drying, with the standard #22 of spraying plant company (Spraying System Company)
J nozzle, inlet temperature are 200～210 ℃, and temperature out is 85～90 ℃.At last spray-dired product is sieved with 40 mesh sieves (aperture is 0.420mm).
Example II
Present embodiment explanation: the aqueous dispersions of the product that obtains in example I is still after the circulation stablely through repeatedly freezing/melting, and inference is stable through being still after prolonging storage period thus.The starch that present embodiment is also illustrated beta-amylase of the present invention degraded is than more stable when the low temperature without the control starch of beta-amylase degraded.
Utilize the method that proposes in the example I, with beta-amylase degraded glutinous corn OSA with through the glutinous corn OSA of the 50WF of acid degradation.With a glutinous corn OSA who transforms through acid in contrast, this derivative is usually used in the drink flavour emulsion now simultaneously, and the starch of beta-amylase degraded is dispersed in the water with 20% solid substance and is placed in the freezing apparatus.In battery of tests, dispersion liquid stands 6 times and freezes/melt circulation, and wherein, the part of freezing in the circulation continues 1～5 day, and full time is 22 days.In another group test, dispersion liquid stands continuous 6 times and freezes/melt circulation, and wherein the part of freezing in the circulation continues 1～5 day, and full time is 18 days.Each freeze/melt circulation after, with a Brookfield viscometer at room temperature (about 22 ℃ (72 °F)) measure viscosity, viscosity is in respect of a #3 axle, per minute rotation 10 times.
The viscosity of contrast increases, and has formed the visible floss, so viscosity degradation.The viscosity of the sample that enzyme was handled is removed when low viscosity and is not almost changed outside the change of Brookfield viscometer reading institute inherent.In addition, freezing/melt the formed floss in circulation back through one in contrast, is non-existent in the sample that enzyme was handled, though through 6 freeze/still do not have the floss appearance after melting circulation.Therefore, the starch component of enzyme liberating shows the bigger anti-effect of bringing back to life in temperature cycle, and inference thus, and it more can replace Sudan Gum-arabic than the contrast composition of present application in beverage.
EXAMPLE III
The present embodiment explanation: treated starch can keep the anti-effect of bringing back to life in storage, and this treated starch is cleaned by removing the maltose that is disengaged by beta-amylase.
The glutinous corn OSA of the beta-amylase degraded of the method preparation that utilizes example I is removed maltose by dialysis.The solid substance ratio of this starch with 15-20% is dispersed in the distilled water, and is placed in the dialysis tube of energy molecular weight cut-off greater than the molecule of 6000-8000 (deriving from Spectropor Membrane).Dispersion liquid to the distilled water dialysis, is not contained any organism in the dialysis thing.Collect starch with ethanol sedimentation then.
The sample that does not contain maltose is placed 5-7 ℃ of refrigeration 83 days together with the maltose sample that contains for preparing in the example I.Sampling is regularly carried out dsc (DSC) and is analyzed with mensuration and make this sample required minimum fate of bringing back to life.Dsc (DSC) analyze be according to A, C.Eliasson at Prog.Biotechnology, " with bringing back to life of determine with dsc method starch " among the 1:93-8 (1985) carried out.
Do not bring back to life after the sample of maltose refrigerates 83 days even do not contain yet.Therefore, as the beta-amylase degraded starch that contains maltose, the starch that does not contain maltose more can resist bring back to life (seeing Table I) than present normally used glutinous corn OSA emulsifying agent.So the existence of maltose is not the essential condition that improves degraded starch stability.
Table I starch
Can be detected with differential scanning calorimeter
The glutinous corn OSA of the fate beta-amylase degraded that 50% starch dispersion liquid is brought back to life is more than 83 days
The myristic acid ester derivant of glutinous corn more than 83 days that transforms through acid of the degraded of glutinous corn OSA derivative beta amylase more than 83 days that transforms through acid of derivative beta amylase degraded does not contain the contrast of glutinous corn OSA derivative more than 83 days of the beta amylase degraded of maltose: glutinous corn OSA derivative contrast in 4 days: the glutinous corn OSA that AMS transforms derivative contrast in 14 days: the glutinous corn OSA derivative that acid transforms contrast in 4 days: the myristinate of the glutinous corn that acid transforms is less than starch that 1 day derivative EXAMPLE IV present embodiment illustrated the beta amylase degraded and more can resists in storage and bring back to life. The aqueous dispersions for preparing 50% solid substance with following starch:the glutinous corn OSA (from the foregoing description II, obtaining) that the acid of the 50WF of glutinous corn OSA (obtaining from the foregoing description I) (2) the beta-amylase degraded of (1) beta-amylase degraded transforms
(3) myristinate of the glutinous corn of the acid conversion of the 50WF of beta-amylase degraded, by following method preparation,
(4) the myristinate control sample of the glutinous corn of the acid of 50WF conversion, by following method preparation,
(5) the glutinous corn OSA control sample of α-Dian Fenmei conversion,
(6) the glutinous corn OSA control sample that transforms of acid and
(7) glutinous corn OSA control sample.
The sample of all beta-amylase degradeds all is to prepare by the method in the example I.All OSA samples all are to prepare by the method in the example I.The myristinate method of sample preparation is: the viscous maize starch that adds the acid conversion of 200 gram 50WF in 300 ml waters makes its pulp, add 3%NaOH with pH regulator to 8.0, in 10 to 15 minutes, add 20 gram N-myristyl-N-Methylimidazole muriates again.Reaction continuity 2 hours when the reaction mixture retrogradation, adds entry again and is beneficial to stir.Filter this reaction mixture, then with the starch resuspending, adjust pH to 5.5, and then filter, with methanol wash and drying.This starch product contains the myristinate of have an appointment 5% (weight).
With these starch suspensions together, place 5～7 ℃ to refrigerate with the sample that does not contain maltose of control sample and top EXAMPLE III.Regularly sampling is estimated its effect of bringing back to life with the dsc in the EXAMPLE III.
Table I has been summarized each starch with dsc analyzing and testing required fate when to a certain degree bringing back to life.
These results show that control sample that beta-amylase of no use handled mixes and bring back to life soon, and the sample of handling can not detect the effect of bringing back to life with dsc analysis in 83 days of studying.
EXAMPLE V
Present embodiment has illustrated various starch and starch derivative presents improved shelf stabilities after the beta-amylase degraded, in some cases, presents the ability of improved formation emulsion.
By the method in the example I, handle one group of starch to form the OSA derivative with octenyl succinic acid anhydride, funnel viscosity was the tapioca (flour) of 33.6 seconds acid conversion when this group starch was included in 19% solid substance and 22 ℃ (72), the W-Gum of 40WF flowability, with a kind of hydroxypropyl, the glutinous corn derivative that the acid of 84WF transforms.5% myristin derivative with a 50WF glutinous corn of the preparation of the method in the EXAMPLE IV.Utilize the hydrocarbon chain ether mixture of 16 carbon to 24 carbon of a viscous maize starch of following method preparation: be about to 100g starch and (derive from the Quab 360 (C of Degussa company with 3 gram 3-chloro-2-hydroxypropyl-16-24 alkyl dimethyl ammonium muriates
16-24H
26-33NOCl
2)) at pH11,5-12 mixes down.Starch mixture is heated to 40 ℃, makes it to react 16 hours, the pH5.5-6 that neutralizes then washes with water 3 times and drying.By the method in the example I with beta-amylase degrade this starch ether derivative (have only an example except), spraying drying then.Exception be the level of control mixture of 16-24 carbon hydrocarbon chain ether of funnel viscosity when the reaction medium viscous maize starch that reaches 50WF the time, promptly stop the Degradation of beta-amylase.This control starch ether is by aforementioned method preparation, but the viscous maize starch of the 50WF that used starting material is a kind of acid to be transformed.
The every other sample of each starch derivative all carries out enzyme liberating and spraying drying by the method in the example I.
Getting the spray-dired starch derivative sample of 20 grams mixes with 180 gram distilled water.This dispersion liquid of stirring at low speed in a Wei Lin Shi mixing machine (Waling blender), powerstat fix on 25-30 to carry out 2 minutes.Get 80 and restrain the center that the citrus oil mixtures are added to vortex lentamente.The citrus oil mixture is the citrus oil of simply squeezing that obtains from Fritzsche DodgeOleott and 3, the 4 parts of ester gum #8BE blendings that obtain from Hercules company by 12 parts.Make starch dispersion liquid with oily emulsification 2 minutes in the stirring of Wei Lin Shi mixing machine high speed.The emulsion that forms is placed in the glass jar, adds a cover, be placed in the freezing apparatus, regularly take out and be warmed up to room temperature.With the separation of visualize emulsion, analyse oil and gelling situation.Remove and when room temperature, can not form outside the stable emulsion, all samples after refrigeration again through test evaluation.
The W-Gum OSA gelling at room temperature that the acid of the 40WF of contrast transforms and do not form emulsion.The viscous maize starch myristinate that the acid of the viscous maize starch that the acid of the 84WF of contrast transforms and the 50WF of contrast transforms forms emulsion, but at room temperature very fast separation.Similarly, the tapioca (flour) of the acid of contrast conversion does not form emulsion yet.The viscous maize starch ether that the acid of the 50WF of contrast transforms forms a bad emulsion, and this emulsion at room temperature is pale yellow cream color, and analyses oil in refrigeration after one day.
On the contrary, the emulsion that the W-Gum OSA of the acid of the 40WF that beta-amylase is degraded conversion forms freezes/melts the separation of circulation back at two, and the emulsion that the tapioca (flour) OSA that is transformed by the acid that beta-amylase is degraded forms is once freezing/melting the separation of circulation back.The hydroxypropylated starch OSA of beta-amylase degraded freezes/melts in the circulation at seven times is stable.The emulsion that is formed by 5% tetradecanoic acid ester derivative of the viscous maize starch of beta-amylase degraded is through once freezing/melt the circulation back and all being stable after three all refrigerations.The emulsion that forms by the viscous maize starch ether of beta-amylase degraded at room temperature and the secondary in 12 days freeze/be still after melting circulation stable.The every other formed emulsion of handling with beta-amylase of sample all is stable in refrigeration after six months.In whole examples, be better than its corresponding contrast with the sample of beta-amylase degraded.
These results show that the starch OSA (for example starch derivative of glutinous corn, corn and cassava etc.) of beta-amylase degraded can improve the package stability of the oil-in-water emulsion that is formed by these starch.No matter starch is to derive (for example OSA) with a kind of hydrophobic/hydrophilic substituent, or only derives (for example myristinate) with a kind of hydrophobic substituent, and its result is identical.In addition, these results are further illustrated in the place that special applications requires, and can use hydroxypropyl viscous maize starch OSA derivative, and the enzyme degradation of this derivative can obtain a kind of oil-in-water emulsion of cryostatic stabilization.
Example VI
Present embodiment shows that treated starch of the present invention stores with the same ability of Sudan Gum-arabic, and is the more anti-storage of emulsifying agent of base-material with starch than what be used for emulsified beverage local flavor oil now.
The glutinous corn OSA that the glutinous corn OSA derivative of enzyme liberating and the acid of 50WF transform prepares by the method in the example I.These starch compositions and comprise the control sample of Sudan Gum-arabic and be generally used for the glutinous corn OSA that the acid in the drink flavour oil emulsion transforms and carry out emulsive by the method for describing in the EXAMPLE V.
With these emulsion refrigerations three months.Before refrigeration beginning and refrigeration after three months with the method in the example II when being 1000 to 5000 centipoises (remove viscosity use #5 axle) mensuration Brookfield viscosity.The sample of the enzyme liberating of visual examination refrigeration after three months shows to have good emulsion stability.The viscosimetric analysis result is summarized in Table II.
Table II
Refrigerate the viscosity emulsifying agent variation in the local flavor oil emulsion after three months
The viscosity of viscosity after three months of beginning
The 160 112OSA derivatives contrast of the glutinous corn of the 1520 1864OSA derivative beta amylases degraded of the glutinous corn of the OSA derivative beta amylase degraded of enzyme 1,256 1576 glutinous corns that the acid of (centipoise) (centipoise) beta amylase degraded transforms: the 160 1880OSA derivatives contrast of the glutinous corn that acid transforms: gum arabic 136 108
These results show that emulsion that the starch composition with beta-amylase degraded makes is with the same variation of ability viscosity, the gelling and analyse oil when storing of Sudan Gum-arabic emulsion.
Therefore, in aqueous dispersions and in emulsion, demonstrate than current known starch emulsifying agent with the treated starch in this claim and in storage, to have improved anti-bringing back to life property and stability.
Example VII A
The preparation method that present embodiment has been illustrated treated starch of the present invention can be undertaken by the reverse order of step in the example I.
Prepare slurries that contain the viscous maize starch of 28% solid substance, add 3% NaOH adjustment PH to 6.0～6.3, spray mashing off down at about 149 ℃ (300 °F).The starch that boils is placed in 55～60 ℃ the water bath with thermostatic control and consistently and stirs.The barley beta-amylase of getting in the example I is added in the starch that boils with per 100 concentration that restrain 1.650DP ° of (butt) starch.Used every milliliter of alpha-amylase activity that contains 0.9Du of this batch beta-amylase in the present embodiment.Degree with the funnel viscosity method control degradation that proposes in the example I.
When starch has reached 30 seconds funnel viscosities, be lower than 3.5～4.0 and make enzymatic inactivation for HCl drops to pH by adding 10, and allow starch remain on this pH value 30～60 minutes.After the passivation, adjust pH to ZO by adding 3%NaOH.
The preparation method of OSA derivative is that per 100 grams (analyse to do and calculate) starch is added to neutral, removes in the starch dispersion liquid of side chain with 3 gram octenyl succinic acid anhydrides, and fully mixed.Reaction is at room temperature proceeded 4 hours, properly stirs simultaneously.
With this starch dispersion liquid of a method spraying drying part of describing in the example I.
By the method in the EXAMPLE V with a kind of commodity emulsifying agent (the glutinous corn OSA derivative that a kind of acid transforms) with the aqueous dispersions specimen preparation citrus oil emulsion of the starch of spray-dired and removal side chain.These emulsion are carried out freezing at least 8 times/melting circulation, and the time is from 1 day to 10 days, estimates then in EXAMPLE V.
The emulsion that forms by control starch through once freeze/melt circulation after, promptly cover the oil film of one deck citrus oil on the surface.On the contrary, remove the emulsion that the starch of side chain forms, through freeze/melt at least 5 times be still after the circulation stable.Be still stable after spray-dired starch sample circulates through 8 times.The lurid oil film of one deck appears in the aqueous dispersion of starch sample when the 6th circulation beginning.
So, in the present invention, use emulsion through the treated starch preparation of enzyme liberating.No matter before or after the preparation starch derivative, in storage, all has improved bringing back to life property and the improved stability of resisting than emulsion with the preparation of commodity starch emulsifying agent.The emulsifying agent and the capsule medium of oil in the material.Using known starch derivative to replace a shortcoming of Sudan Gum-arabic is that these known starch derivative are unstable in storage.These starch derivative are short and refrigeration and freeze and unfreeze poor stability than the shelf-life of Sudan Gum-arabic.So in some applications, when for example being used as local flavor syrup base-material in the production of soft drink and similar beverage, these starch are derived substituent not as good as Sudan Gum-arabic.Carry out bottledly because the drink manufacturing merchant is transported to different areas with local flavor syrup base-material, and these syrup base-materials may be through refrigeration for a long time, so these local flavors oil emulsion must keep stablizing in storage before filling bottle operation.In addition, because different filling bottle merchants' refrigerating temperature may be different, or one day may be different with the refrigerating temperature of another day, so the alternately variation that local flavor oil emulsion must the ability temperature, comprise freeze-thaw cycle.
The stability problem that occurs in beverage application is because starchbased product has (retrograde) tendency of bringing back to life, and local flavor oil emulsion is replaced in variation or the long storage in temperature destroy.When serious, starch may be brought back to life and be formed a kind of gel, and local flavor oil is separated from aqueous phase fully.The effect of bringing back to life of starch comes down to a crystallisation process, and it is to produce when the linear fraction of starch molecule forms the interchain hydrogen bond during series arrangement and by hydroxyl each other.When having produced enough interchain keys, molecular association is to form molecule aggregates, and these aggregates have the ability that reduces hydration, therefore shows lower water-soluble.These aggregates may precipitate, and perhaps, in denseer solution, may form a kind of gel.This trend of bringing back to life is more remarkable in the starch that contains more line style amylose molecule.Contain at the same time in the starch of amylose starch and amylopectin, or only in the starch of branched molecule, this tendency of bringing back to life is more not remarkable, when temperature descended, the starch that contains amylose starch and amylopectin simultaneously showed the bigger tendency of bringing back to life.
In some applications, partly overcome the effect of bringing back to life by chemical method derivatized starch molecule, also promptly make starch stable, when storing, reduce the tendency that starch loses hydratability thereby reach by the association between the starch molecule or with the association between the different piece of a part.For example, available a kind of reagent is introduced some substituting groups with starch reaction, as hydroxypropyl, and phosphoric acid ester, groups such as acetic ester or succinate are with stabilizing starch molecule in storage.This derivatization reaction can recur on starch, thereby further improves to obtain to have the starch of special purpose by crosslinked or degraded.But these deutero-starch do not have typical stable emulsifying property as Sudan Gum-arabic.
Other known methods that can limit starch retrogradation at low temperatures can not provide stable emulsified starch.For example, (Wurzburg's etc.) United States Patent (USP) 3 that on August 25th, 1970 announced, 525, disclose for No. 672 with a kind of enzyme (for example beta-amylase) and handled starch thickener crosslinked, that suppress, the starch thickener of other thickening food products of storage has freeze-thaw stability thereby be used in pie filling, pudding and need at low temperatures.Remove outside the above-mentioned inhibition method, partly the derivatized starch base-material also is favourable sometimes.Typical substituting group comprises ester group such as groups such as acetic ester, succinate, phosphoric acid ester and sulfuric ester, and other groups.
(Wurzburg's etc.) United States Patent (USP) that on January 31st, 1984 announced discloses a kind of glutinous property cereal starch thickening material for 4,428, No. 972, and it can have good especially low-temperature stability in aqueous dispersion, and this starch derives from a kind of WXSU
2Genotypic plant.
But, being used for overcoming in the invention of the low tempertaure storage effect of bringing back to life at all these, the disclosed starchbased product of none can be used for preparing the oil-in-water emulsion of shelf-stable.Therefore, need a kind of product, it had both had emulsifying property, can store at shelf again, keep stable in the refrigeration, freeze-thaw cycle, and this product can be used for replacing Sudan Gum-arabic.
Therefore, need a kind of improved treated starch, it has the stable emulsification property of Sudan Gum-arabic.The invention provides a kind of like this treated starch, the method for producing this treated starch also is provided simultaneously.
The product that contains starch emulsion also is provided here, and these products have good shelf stabilities, are the food and drink that contain local flavor oil emulsion specifically.
The invention provides a kind of treated starch with emulsifying property, the emulsion of this treated starch has improved stability, and ability is analysed oil and anti-agglomerative characteristic when storing.This treated starch comprises a kind of starch derivative that contains a hydrophobic group or contain a hydrophilic group and a hydrophobic group simultaneously, wherein degraded by a kind of exoenzyme up to 70% starch derivative by weight, this exoenzyme can be from the non-reducing end fracture 1 of starch, 4-α-D-glycosidic link, but can not rupture 1 of starch, 6-α-D glycosidic link.
The method that the present invention also provides a kind of preparation to have the treated starch of emulsifying property, the emulsion of this treated starch has improved stability, and ability is analysed oil and agglomerative characteristic in storage.This method may further comprise the steps: a) prepare a kind of starch derivative of gelatinization, the characteristic of this derivative is for all containing a hydrophobic group or contain a hydrophilic group simultaneously and a hydrophobic group on each substituting group; B) will be degraded to maltose up to the starch derivative of 70% (by weight) with a kind of exoenzyme, this outer endonuclease capable ruptures 1 from the non-reducing end of starch, 4-α-D glycosidic link, but can not rupture 1 of starch, 6-α-D glycosidic link.
Used enzyme is handled at starch and is carried out after containing hydrophobic group or containing hydrophilic group and hydrophobic group simultaneously through deriving in the inventive method, thereby makes it have emulsifying property.Perhaps, also can carry out enzyme before the preparation starch derivative handles.Prepare in the United States Patent (USP) 2,661,349 that the method for this analog derivative mentions in front open.Best starch derivative is a kind of starch alkenyl succinic acid half ester, and carboxyl wherein can be a kind of acid or a kind of carboxylicesters.But, it should be noted anyly can on starch molecule, produce required hydrophobic function or hydrophobic and hydrophilic dual-use function, thereby the method that makes this treated starch have emulsifying property can be used for preparing treated starch of the present invention.The method that (Trzasko's etc.) United States Patent (USP) of announcing on December 2nd, 1986 discloses suitable derivative and prepared these derivatives for 4,626, No. 288.
Can rupture 1 at the non-reducing end of starch molecule with a kind of, 4-α-D-glycosidic link but 1 of the starch molecule that can not rupture, the exoenzyme of 6-α-D-glycosidic link is handled the starch derivative that contains a hydrophobic group or contain a hydrophilic group and a hydrophobic group simultaneously, and the starch derivative of (preferably 55%) (weight) is degraded to maltose up to 70%.
In preparation modification degraded starch of the present invention, require starch to form the concentration that is suitable for end-use of soup compound with any required ratio with water to reach desired enzyme-substrate concentration or to calculate.Heat this mixture then and make starch pasting.If desired, also can use granular starch, but the enzymolysis process of granular starch carries out slowly.Then the temperature of mixture and pH are transferred to the manufacturer of the certain enzyme that is used to prepare starch product or the optimum value that the supplier recommends.
This kind of enzyme must be a kind of exoenzyme, and it can disconnect 1 from the non-reducing end of starch molecule, 4-α-D glycosidic link, but can not disconnect 1,6-α-D glycosidic link.Beta-amylase preferably, it is a kind of very special exoenzyme, by it, effect, can only form a kind of reaction complex compound at the non-reducing end of the starch molecule that has Fructus Hordei Germinatus glucoside base, this Fructus Hordei Germinatus glucoside base is by 1, and 4-α-D glycosidic link is with the glucosyl group bonding.Like this, enzyme can only be at the same starch reaction of non-aldehyde end (non-reducing end), thereby splits the maltose unit from these outside chain interruptions, until reaching tapping point (1,6 key).After enzyme is handled, still residual maltose or glucose unit on each tapping point of starch molecule.Because this outer endonuclease capable disconnects 1,4 key of starch molecule, but can not disconnect 1,6 key, therefore the residue after the degraded has a molecular structure closely, and this structure does not have outside side chain basically or has only short outside side chain.Like this, the outside side chain that product is just not long, the outside side chain of this length can cause effect of bringing back to life and synersis, described starch water-dispersion in the aqueous dispersion of starch
Through long storage and/or multigelation circulation.
Allow the starch of enzymic digestion starch up to 70% (be preferably and reach 55%) (weight)
Claims (6)
1. treated starch with emulsifying property, its emulsion has improved stability and anti-oil and the anti-agglomerative characteristic analysed in storage, this treated starch comprises a kind of starch derivative that contains a hydrophobic group or contain a hydrophilic group and a hydrophobic group simultaneously, have in this derivative until 70% (weight) by enzyme liberating outside a kind of, this outer endonuclease capable disconnects 1 from the non-reducing end of starch, 4-α-D-glycosidic link, but can not disconnect 1 of starch, 6-α-D-glycosidic link, described hydrophobic group comprise alkyl or the alkenyl that contains 5-24 carbon atom.
2. the treated starch of claim 1 is characterized in that described exoenzyme is a beta-amylase, and described starch is a kind of viscous maize starch, and the gelatinization of this starch and used at least 0.25% (calculating) by the starch dry weight the octenyl succinic acid anhydride processing and derive.
Claim 2 change living starch, it is characterized in that described starch is further derived and contained hydroxypropyl.
4. the treated starch of claim 1 is characterized in that the described starch derivative of a hydrophobic group that contains is through gelatinization.
5. method that is used to prepare treated starch with emulsifying property, the emulsion of this starch has improved stability and anti-oil and the anti-agglomerative characteristic analysed in storage, this method may further comprise the steps: the starch derivative of (a) preparing a kind of gelatinization, the characteristic of this derivative is that each substituting group all contains a hydrophobic group or contains a hydrophilic group simultaneously and a hydrophobic group, and this hydrophobic group comprises alkyl or the alkenyl that contains 5-24 carbon atom; (b) with a kind of exoenzyme with this starch derivative be degraded to maltose until 70% (weight), described exoenzyme can disconnect 1 from the non-reducing end of starch, 4-α-D-glycosidic link, but can not disconnect 1 of starch, 6-α-D-glycosidic link.
6. method that is used to prepare treated starch with emulsifying property, the emulsion of this starch has improved stability and anti-oil and the anti-agglomerative characteristic analysed in storage, this method may further comprise the steps: (a) with a kind of outer enzyme liberating pasted starch, pasted starch until 70% (weight) is degraded to maltose, described exoenzyme can disconnect 1 from the non-reducing end of starch, 4-α-D-glycosidic link, but 1 of starch can not be disconnected, 6-α-D-glycosidic link; (b) starch reaction of enzyme liberating is to provide a kind of starch derivative that contains a hydrophobic group or contain a hydrophilic group and a hydrophobic group simultaneously therewith with a kind of reagent, and this hydrophobic group comprises alkyl or the alkenyl that contains 5-24 carbon atom.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US234,070 | 1988-08-18 | ||
| US07/234,070 US4977252A (en) | 1988-03-11 | 1988-08-18 | Modified starch emulsifier characterized by shelf stability |
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| Publication Number | Publication Date |
|---|---|
| CN1040374A CN1040374A (en) | 1990-03-14 |
| CN1034578C true CN1034578C (en) | 1997-04-16 |
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| CN89105576A Expired - Lifetime CN1034578C (en) | 1988-08-18 | 1989-08-15 | Modified starch emulsifier characterized by shelf stability |
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| JP (1) | JP2540204B2 (en) |
| CN (1) | CN1034578C (en) |
| AU (1) | AU607071B2 (en) |
| IL (1) | IL90061A0 (en) |
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| US11612578B2 (en) | 2016-11-16 | 2023-03-28 | Fresenius Kabi Deutschland Gmbh | Nutritional composition for use in therapy of patients with sarcopenia and/or frailty or pre-sarcopenic and/or pre-frail patients |
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| EP0967540A3 (en) * | 1998-06-26 | 2002-09-04 | Wacom Co., Ltd. | Digitizer system with cursor shape change |
| US6447615B2 (en) * | 1999-08-10 | 2002-09-10 | National Starch And Chemical Investment Holding Corporation | Sago fluidity starch and use thereof |
| US8252322B2 (en) * | 2003-06-03 | 2012-08-28 | Corn Products Development, Inc. | Delivery system with increased bioavailability |
| US20050208009A1 (en) * | 2004-03-22 | 2005-09-22 | Valerie Bonnardel | Emulsifier |
| EP1743693B1 (en) * | 2005-07-12 | 2017-03-29 | Coöperatie Avebe U.A. | Emulsifier |
| EP1981357B1 (en) * | 2006-02-06 | 2012-10-24 | DSM IP Assets B.V. | COMPOSITIONS CONTAINING ß-CAROTENE |
| JP5033553B2 (en) * | 2006-09-15 | 2012-09-26 | フタムラ化学株式会社 | Emulsification stabilizer |
| US11173106B2 (en) | 2009-10-07 | 2021-11-16 | Johnson & Johnson Consumer Inc. | Compositions comprising a superhydrophilic amphiphilic copolymer and a micellar thickener |
| US8258250B2 (en) | 2009-10-07 | 2012-09-04 | Johnson & Johnson Consumer Companies, Inc. | Compositions comprising superhydrophilic amphiphilic copolymers and methods of use thereof |
| EP2486063B1 (en) * | 2009-10-07 | 2018-03-28 | Akzo Nobel Chemicals International B.V. | Superhydrophilic amphiphilic copolymers and processes for making the same |
| US8399590B2 (en) | 2009-10-07 | 2013-03-19 | Akzo Nobel Chemicals International B.V. | Superhydrophilic amphiphilic copolymers and processes for making the same |
| US20110124746A1 (en) * | 2009-11-25 | 2011-05-26 | National Starch & Chemical Company | Alkenyl succinic acid anhydride half ester emulsifier |
| CN102134282B (en) * | 2011-01-07 | 2013-03-20 | 华南理工大学 | Composite modified starch of hydroxypropyl and alkenyl succinic acid and preparation method and application thereof |
| CN103386136B (en) * | 2013-07-31 | 2015-05-13 | 西南大学 | Application of hydrophobic glucan in preparation of curcumin solubilizing agent and utilization method of hydrophobic glucan |
| CN105481988B (en) * | 2016-01-12 | 2018-01-30 | 神州富盛科技（北京）有限公司 | A kind of modified starch with high embedding rate |
| CN105602749B (en) * | 2016-02-17 | 2018-10-23 | 神州富盛科技（北京）有限公司 | A kind of Longaacting fragrance-aretaining agent |
| CN108409872B (en) * | 2018-03-16 | 2021-05-11 | 江南大学 | Preparation method of octenyl succinic anhydride modified starch ester by double-enzyme enzymatic hydrolysis |
| EP4149280A1 (en) * | 2020-05-14 | 2023-03-22 | International Flavors & Fragrances Inc. | Robust flavor emulsions |
| CN111955705A (en) * | 2020-08-25 | 2020-11-20 | 上海膳维奇生物科技有限公司 | Low-oil-separation sauce |
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| GB1160356A (en) * | 1967-02-17 | 1969-08-06 | Nat Starch Chem Corp | Improvements in or relating to Methods for Preparing Starch Products. |
| GB1171893A (en) * | 1967-06-07 | 1969-11-26 | Cooperative Verkop En Producti | Process for the Preparation of Novel Starch Products |
| US4035235A (en) * | 1973-03-12 | 1977-07-12 | Anheuser-Busch, Incorporated | Method of making lipophilic starch derivatives |
| US4551177A (en) * | 1984-04-23 | 1985-11-05 | National Starch And Chemical Corporation | Compressible starches as binders for tablets or capsules |
| US4670268A (en) * | 1985-01-29 | 1987-06-02 | Abbott Laboratories | Enteral nutritional hypoallergenic formula |
-
1989
- 1989-04-14 JP JP1093314A patent/JP2540204B2/en not_active Expired - Lifetime
- 1989-04-24 IL IL90061A patent/IL90061A0/en not_active IP Right Cessation
- 1989-05-12 AU AU34762/89A patent/AU607071B2/en not_active Ceased
- 1989-08-15 CN CN89105576A patent/CN1034578C/en not_active Expired - Lifetime
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| GB1160356A (en) * | 1967-02-17 | 1969-08-06 | Nat Starch Chem Corp | Improvements in or relating to Methods for Preparing Starch Products. |
| GB1171893A (en) * | 1967-06-07 | 1969-11-26 | Cooperative Verkop En Producti | Process for the Preparation of Novel Starch Products |
| US4035235A (en) * | 1973-03-12 | 1977-07-12 | Anheuser-Busch, Incorporated | Method of making lipophilic starch derivatives |
| US4551177A (en) * | 1984-04-23 | 1985-11-05 | National Starch And Chemical Corporation | Compressible starches as binders for tablets or capsules |
| US4551177B1 (en) * | 1984-04-23 | 1986-12-23 | ||
| US4670268A (en) * | 1985-01-29 | 1987-06-02 | Abbott Laboratories | Enteral nutritional hypoallergenic formula |
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| US11612578B2 (en) | 2016-11-16 | 2023-03-28 | Fresenius Kabi Deutschland Gmbh | Nutritional composition for use in therapy of patients with sarcopenia and/or frailty or pre-sarcopenic and/or pre-frail patients |
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| JPH0255702A (en) | 1990-02-26 |
| AU3476289A (en) | 1990-02-22 |
| JP2540204B2 (en) | 1996-10-02 |
| AU607071B2 (en) | 1991-02-21 |
| CN1040374A (en) | 1990-03-14 |
| IL90061A0 (en) | 1989-12-15 |
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