CN106455640A - Stabilized micellar casein and compositions - Google Patents

Stabilized micellar casein and compositions Download PDF

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Publication number
CN106455640A
CN106455640A CN201580028792.6A CN201580028792A CN106455640A CN 106455640 A CN106455640 A CN 106455640A CN 201580028792 A CN201580028792 A CN 201580028792A CN 106455640 A CN106455640 A CN 106455640A
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China
Prior art keywords
composition
weight
protein
albumen
micellar casein
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Chinese (zh)
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E·J·P·德考特
J·布纳万
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Nutricia NV
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Nutricia NV
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    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L2/00Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
    • A23L2/52Adding ingredients
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23CDAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING THEREOF
    • A23C9/00Milk preparations; Milk powder or milk powder preparations
    • A23C9/12Fermented milk preparations; Treatment using microorganisms or enzymes
    • A23C9/1203Addition of, or treatment with, enzymes or microorganisms other than lactobacteriaceae
    • A23C9/1216Other enzymes
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23JPROTEIN COMPOSITIONS FOR FOODSTUFFS; WORKING-UP PROTEINS FOR FOODSTUFFS; PHOSPHATIDE COMPOSITIONS FOR FOODSTUFFS
    • A23J3/00Working-up of proteins for foodstuffs
    • A23J3/04Animal proteins
    • A23J3/08Dairy proteins
    • A23J3/10Casein
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L2/00Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
    • A23L2/52Adding ingredients
    • A23L2/66Proteins
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L33/00Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/10Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
    • A23L33/17Amino acids, peptides or proteins
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L33/00Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/10Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
    • A23L33/17Amino acids, peptides or proteins
    • A23L33/19Dairy proteins
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L33/00Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/40Complete food formulations for specific consumer groups or specific purposes, e.g. infant formula
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23CDAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING THEREOF
    • A23C9/00Milk preparations; Milk powder or milk powder preparations
    • A23C9/14Milk preparations; Milk powder or milk powder preparations in which the chemical composition of the milk is modified by non-chemical treatment
    • A23C9/142Milk preparations; Milk powder or milk powder preparations in which the chemical composition of the milk is modified by non-chemical treatment by dialysis, reverse osmosis or ultrafiltration
    • A23C9/1422Milk preparations; Milk powder or milk powder preparations in which the chemical composition of the milk is modified by non-chemical treatment by dialysis, reverse osmosis or ultrafiltration by ultrafiltration, microfiltration or diafiltration of milk, e.g. for separating protein and lactose; Treatment of the UF permeate
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23VINDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00Food compositions, function of food ingredients or processes for food or foodstuffs
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12YENZYMES
    • C12Y203/00Acyltransferases (2.3)
    • C12Y203/02Aminoacyltransferases (2.3.2)
    • C12Y203/02013Protein-glutamine gamma-glutamyltransferase (2.3.2.13), i.e. transglutaminase or factor XIII

Abstract

The invention pertains to a liquid composition comprising protein, wherein the protein concentration is between 11 and 25 g per 100 ml, said composition comprising cross-linked micellar casein, wherein the composition is preferably heat-treated by heat sterilization or pasteurization.

Description

Stable micellar casein and composition
Technical field
In general, the present invention relates to a kind of liquid enteral composition for providing nutrition, it is as replenishers or work For complete nutrient, and it has high protein concentration and high energy content.
Background technology
The ability of product designed for old people can gradually weaken.Because they need to eat too substantial amounts of product to meet daily Nutrient intake, so they may have any problem in terms of consumable products.Therefore, compliance is not optimal, and generally, takes the photograph It is not good enough for entering thing, thus leading to not good enough nutrition.Therefore, the elderly and Disease need the energy with increase and every The nutrient liquid composition of the more concentration of albumen that UD increases.
Some morbid states or illness may need to limit the diet of edible for patients.For example, kidney patients may need liquid Body restrictive diet.Equally, many patients need liquid volume nutriment as minimum as possible.Such patient may with Cancer or the cachexia for the treatment of of cancer correlation, or with serious PUD D such as COPD (COPD), tuberculosis Disease and animal infectious diease, or the people of experience major surgery or wound (as burnt).Additionally, suffering from throat or mouth disease The people of (as the cancer of the esophagus or stomatitis) needs special liquid, corpusculum with the people (as the people of dysphagia) with the problem of swallowing Long-pending nutriment.Additionally, many patients are reduced and/or ageusia by appetite due to their disease, and also will benefit from Energy and the intensive small volumes of liquids alimentation composition of albumen.
However, when the calorie in the fluid composition that has additional nutrients and/or protein concentration, which increasing integral product Viscosity and stability, and this has adverse effect to the palatability of composition.Furthermore, it is possible to mixing or being even bound to egg White mineral matter can by the mineral level in the product with the protein concentration of increase improve to acceptable nutritional limits with On.Increased viscosity can make liquid nutritional compositions be difficult to edible or take, and also the taste of composition can be made to weaken.This Outward, the stability of the fluid product of such albumen and energy-intensive is likely to become problem;The shape of the salt crystal in shelf life Become to be likely to become problem, and expect that this medical nutritious product has at least 9 months, the shelf life of preferably at least 1 year.
WO 02/098242A1 discloses one kind and is based on (60:40) soy protein isolate/caseinic acid salt mixture The liquid oral replenishers (2.25kcal/ml) of heat-dense, its have the protein level of 9g/100ml (16 energy %), The fat (49 energy %) of 12.25g/100ml and the digestible carbohydrate (35 energy %) of 19.7g/100ml.According to WO 02/098242, because caseinate can improve the viscosity of replenishers, so need caseinate and soybean protein to divide Mixture from thing.Do not solve the impact of heat endurance.
CA2310659 A1 (NESTLE SA [CH]) discloses TGase for accelerating the use of proteopepsis speed On the way.Embodiment 1 shows the micellar casein solution of 10 weight % through transglutamin-ase 9 ferment treatment, but this solution does not exist In comprise further carbohydrate and fat and there is high protein content nutrition product in.Composition not glue under pH 3 Change, but whether there is no with regard to composition the information of sufficiently low viscosity.It is unlikely to be and inactivated turn due to heat treatment Glutaminase, and make the product in CA2310659 have at least shelf life of 9 months.The product of embodiment 1 is merely used as Preparation has the intermediate of other nutrition embodiments of low protein level.For example, embodiment 4 discloses a kind of infant formula, It has the casein of the albumen 40%TG process of the energy content of 70kcal/100ml and 2.3 grams of embodiments 1.Do not pay close attention to and also have There are the stability problem of high-protein nutrient product of high energy content and the correlation of the micronutrient content of described composition Consequence.
US 5683984 and corresponding EP0686396B1 teaches and substitutes medium energy nutrition system with natural micellar casein All caseinates in agent (1kcal/ml), mainly comprise natural micellar casein and have low viscosity and can hold to obtain The preparation of the heat endurance being sterilized.It discloses a kind of containing the caseic composition of natural micella being 7 volumes % to the maximum. Do not pay close attention to the problem of high-energy and the impact of other compositions and mineral matter, fail to disclose how the battalion in high energy high protein yet Stablize micellar casein in foster preparation.It had not both implied the problem that will appear from, and did not instruct bad shelf stabilities and heat yet Stability, not to mention the measure of the open described problem overcoming preparation.
WO2009/072885 [NV Nutricia] discloses a kind of liquid enteral nutritional composition of sterilizing, every 100ml Described composition comprise 6 to 14g albumen, described albumen includes micellar casein and caseinate, the energy of described composition Metric density is at least 2.0kcal/ml.Obtain a kind of low viscous product of high protein of shelf-stable.WO2009/072885's is interior Hold here to include in the way of being cited herein.By using micellar casein and caseinate, the prior art file illustrates The alimentation composition based on little specific volume micellar casein can be prepared.The micella of these highly denses allows to liquid group Add more albumen in compound, form the negative consequence of (deposit) without increasing viscosity or particle.
However, the shortcoming of micellar casein is this albumen at different places in composition disclosed in above-mentioned prior art Relatively unstable under the conditions of reason.Additionally, other compositions such as carbohydrate, fat and micronutrient further limit glue Restraint caseic use, particularly in meeting the nutrition complete combination thing of daily mineral matter intake of recommendation.All these Composition, is especially in the presence of in these compositions the monovalence of (and in micellar casein) and divalent ion to caseic micellar structure There is significant destabilization.Regrettably, casein micelles structure is sensitive to physicochemical change, is easily subjected to locate The change managed step and lead to and the impact of the change of Product environment (such as pH or temperature), and the mineral matter of final products is contained Amount (ionic strength) and mineral origin are sensitive.Divalence sun in sodium present in composition and/or potassium and casein micelles from Son exchanges.This replacement of bivalent cation will make micella unstable, and it makes micella particle diameter increase and becomes not compact.Class As, be present in chelating agent such as citrate in composition and phosphate (for example as pH buffer) by with carry out arrogant glue The bivalent cation of binding structure combines and so that them is reduced and have destabilization to micella.These factors above-mentioned will be to product Heat endurance, viscosity and shelf stabilities have adverse effect.
Therefore, it is an object of the invention to provide a kind of more shelf-stable, thermally-stabilised, attractive, good to eat low viscosity Liquid enteral composition, it is less sensitive to physiological change or chemical change, is adapted as replenishers or as complete nutrient Behave, particularly the elderly or patient provides nutrition, it has preferably at least 1.0kcal/ml, more preferably at least 1.5kcal/ml High energy content and at least protein content of 8g/100ml.
Content of the invention
For this reason, the inventors discovered that in the new nutrition being suitable for prepare the alimentation composition of albumen and energy-intensive Available solution.The present inventor expects being used for crosslinked micellar casein using the solution of TGase enzymatic activity.It has been found that In micella, casein micella makes these casein micelles more stable and to subsequent treatment conditions or ionic conditions less Sensitive.Appended experiment and accompanying drawing confirm these stablizing effects.The present inventor's application TGase [TG] is processed to prepare There is at least high protein density of 8g/100ml and the preferably at least high energy content of 1.5kcal/ml and have stablizing of improvement The nutrition product of property.
During the last ten years it is known that the casein micelles in breast can carry out crosslinking using TG process, to improve the thermally-stabilised of breast Property, it is believed that these stabilizations are retained because of lower protein concentration.With reference to Smiddy et al. " Stability of casein micelles cross-linked by trans glutaminase”J.Dairy Sci.89:1906-1914, its Disclose TGase for the use of the casein micelles in stable newborn (there is about 3.2% relatively low protein content) On the way.The increase of expected protein concentration is crosslinked (because the degree of approach of albumen increases) in micella by stimulating crosslinking between micella to exceed, and And crosslinking will lead to the viscosity of micellar aggregates, proteinosis and therefore worse product stability and increase between such micella And/or quality.
However, the inventors discovered that making crosslinking in micella exceed crosslinked mode between micella, so that the glue of crosslinking Bundle casein compared with its noncrosslinking homologue, there is higher temperature stability and absolute acid stability, or even have more than 8g, The preferably greater than protein content of 11g albumen/100ml, and the preferably greater than energy density of 1.0kcal/100ml.In addition, making us Surprisingly it has been found that, can prepare to have and produce more than the stable liquid of 14 grams, the up to very high protein content of 25g/100ml Product, it is higher than the density of presently commercially available product.These can be applied to find to reduce picked-up volume, because the present inventor also sends out Existing, when product has less volume (less than 150ml), with (and bigger dose of 200ml dosage commonly used in the art Amount) compare, compliance -- compliance particularly in above-mentioned target subject -- and be improved.
It is surprising that also finding when removing calcium and/or phosphorus from casein -- for example oozed by combining ultrafiltration Filter, electrodialysis or ion-exchange chromatography, the structure of crosslinked micellar casein is unaffected.This makes it can still benefit from The tight structure of casein micelles, and there is not calcium and/or the phosphorus of higher level in the composition.It is true that as appended experiment Partly shown, when remove substantial amounts of calcium and/or phosphorus, preferably both when, can further improve heat endurance.Micellar casein In calcium concentration higher than the calcium concentration in casein sodium about 20 times.In the micellar casein of transglutamin-ase 9 ferment treatment, calcium Concentration can reduce 10-50% to the casein sodium that equivalent is used as low level as during protein sources, thus can obtain Arrive the low viscosity nutrition containing 8 to 25g/100ml albumen, preferably 11 to 25g/100ml albumen and low-level calcium and/or phosphorus Product.
The concentration of calcium is preferably shorter than 2200mg/100g albumen (more preferably less than 1000mg/100g albumen, more preferably less than 500mg/100g albumen), and the relative quantity of phosphorus is preferably shorter than 1550mg/100g albumen, more preferably less than 1250mg/100g egg In vain, it is more preferably less than 300mg/100g albumen.In a preferred embodiment, described composition comprise 8 to 25g albumen, More preferably 11 to 25g albumen/100ml, and its calcium concentration is less than 50mg/g albumen, more preferably less than 20mg/g albumen, preferably Less than 15mg/g albumen, even more preferably 5 to 20.0mg.In one embodiment, every gram of albumen contains 1 to 15mg calcium.? In one embodiment, calcium concentration is less than 5mg/g albumen, preferably 0.2-5mg calcium/g albumen, more preferably 0.2-4.0mg calcium/g egg In vain.The preferred composition of the present invention is often comprised at least 8g albumen/100ml, more preferably at least 11g albumen/100ml, and energy Amount content is at least 100kcal/100ml, and wherein calcium concentration is less than 210mg, preferably shorter than 175mg, is even more preferably less than 120mg, most preferably less than 80mg/100kcal.
In one embodiment, the albumen in described composition comprises at least 80% casein and caseinate, And less than 20%, the another kind of more preferably less than 10 weight % be selected from the albumen of whey and vegetable protein, based on total protein weight Gauge, and wherein calcium concentration be preferably shorter than 2200mg/100g albumen (more preferably less than 1000mg/100g albumen, more preferably Less than 500mg/100g albumen), and the relative quantity of phosphorus is preferably shorter than 1550mg/100g albumen (more preferably less than 1250mg/ 100g albumen, even more preferably less than 300mg/100g albumen).In a preferred embodiment, described composition comprises 8 To 25g albumen/100ml, more preferably comprise 11 to 25g albumen/100ml, preferably there is aforementioned restriction, that is, be less than 20%, more excellent The another kind less than 10% for the choosing is selected from the albumen of whey and vegetable protein, and based on total protein by weight meter, and its calcium concentration is less than 50mg/g albumen, more preferably less than 20mg/g albumen, preferably shorter than 15mg/g albumen and even more preferably 5 to 20.0mg/g egg In vain, and most preferably 1 to 15mg calcium/g albumen.In one embodiment, calcium concentration is less than 5mg/g albumen, preferably 0.2-5mg Calcium/g albumen, more preferably 0.2-4.0mg calcium/g albumen.Root invention a kind of preferred composition will comprise at least 8g albumen/ 100ml, more preferably at least 11g albumen/100ml, and energy content is at least 100kcal/100ml, and wherein calcium concentration is less than 210mg/100kcal, preferably shorter than 175mg/100kcal, even more preferably less than 120mg/100kcal, most preferably less than 80mg/100kcal, and described albumen comprises at least 80% casein and caseinate, and less than 20%, more preferably It is selected from the albumen of whey and vegetable protein less than the another kind of 10 weight %, based on total protein by weight meter.
Preferred embodiment list
1. the protein-contg fluid composition of a kind of bag, wherein protein concentration are 8 to 25g/100ml, and described composition comprises Crosslinked micellar casein, wherein preferably passes through heat sterilization or pasteurization, preferred heat sterilization to comprising described crosslinking The composition of micellar casein is heat-treated.
2. the protein-contg fluid composition of a kind of bag, wherein protein concentration are 8 to 25g/100ml, and described composition comprises Crosslinked micellar casein, wherein said albumen comprises based on total protein meter at least 30 weight %, preferably at least 50 weight %, more Preferably at least 70 weight %, the micellar casein of most preferably at least 85 weight %, wherein preferably at least part micellar casein is Crosslinked, and wherein preferably by heat sterilization or pasteurization, preferred heat sterilization, described composition is heat-treated.
3. the composition of embodiment 1 or 2, it comprises 11 to 25g albumen/100ml.
4. the fluid composition of any one of foregoing embodiments, it also comprises fatty and digestible carbohydrate, And wherein said albumen comprises the crosslinked micellar casein based on total protein meter at least 30 weight %.
5. the fluid composition of any one of foregoing embodiments, wherein said albumen comprises the friendship of 35 to 100 weight % The micellar casein of connection.
6. the fluid composition of any one of foregoing embodiments, the energy density of wherein said composition is at least 1.0kcal/ml, preferably at least 1.5kcal/ml and even more preferably 2.0 to 3.0kcal.
7. the fluid composition of any one of foregoing embodiments, is wherein based on total protein content meter, and calcium concentration is less than 2.6 Weight %, preferably shorter than 1.5 weight %, preferably shorter than 0.4 weight %.
8. the fluid composition of any one of foregoing embodiments, wherein said composition is at 20 DEG C and 100s-1Shearing Under rate, measured viscosity for 5mPa.s to 500mPa.s, preferably 5 to 200mPa.s is.
9. the fluid composition of any one of foregoing embodiments, wherein said composition also comprises casein sodium, junket Protein acid calcium, magnesium caseinate or Caseins, potassium salts, or its mixture, preferably casein sodium or Caseins, potassium salts or both.
10. the fluid composition of any one of foregoing embodiments, it also comprises at least one vegetable protein, preferably at least A kind of vegetable protein selected from pea protein, soybean protein, wheat gluten, potato protein or zein.
The fluid composition of any one of 11. foregoing embodiments, it comprises the gross weight meter based on albumen in composition Less than 1.6 weight %, preferably smaller than 1.3 weight %, more preferably less than 0.25 weight % phosphorus.
The fluid composition of any one of 12. foregoing embodiments, its comprise at least 11g, preferably at least 12g albumen/ 100ml, even more preferably 12 to 20g albumen/100ml.
A kind of 13. methods preparing the composition of micellar casein comprising crosslinking, it includes:A () provides a kind of pH is 6 To 8 fluid composition, it comprises gross weight meter 7 to 15 weight % based on composition, the micella junket of preferably 8 to 10 weight % Albumen;B () carries out transglutamin-ase 9 ferment treatment to described composition, preferably at a temperature of 37 DEG C to 50 DEG C, preferably about 45 At DEG C, to obtain the composition of the micellar casein comprising crosslinking;(c) optionally pH is adjusted to higher than 6.6 and/or to group Compound carries out enzyme inactivation, and wherein described in preferred pair, composition carries out heat sterilization or pasteurization, preferred heat sterilization.
The method of 14. embodiments 13, wherein enters to the composition of the micellar casein comprising crosslinking obtaining in (b) Row filters, and wherein after filtration, preferred pair composition carries out dialysis.
The method of 15. embodiments 13 or 14, wherein transglutamin-ase 9 ferment treatment include making composition at said temperatures With at least 0.05 weight %, preferred 0.1-0.55 weight %, more preferably 0.1-0.35 weight % TGase contact excellent Choosing at least 1 hour, 0.5 to 24 hour, preferably 1 to 5 hour, more preferably 2 to 4 hours.
The method of any one of 16. embodiments 13-15, wherein by crosslinked micellar casein composition drying to be formed Powder, it is preferred to use spray drying process.
A kind of 17. compositions of the micellar casein comprising crosslinking, it can pass through the side of any one of embodiment 13-16 Method obtains.
A kind of 18. powder compositions, it comprises the micella junket egg of the crosslinking based on powder gross weight meter at least 30 weight % In vain.
The powder of 19. embodiments 18, it comprises the micella junket of the crosslinking based on powder gross weight meter 90-100 weight % Albumen.
The powder of 20. embodiments 18 or 19, it comprises to be less than the calcium of 0.8 weight % based on total protein content meter.
The powder of 21. embodiments 18-20, it comprises the phosphorus less than 1.4 weight %, the phosphorus of preferably smaller than 0.4 weight %.
The powder of 22. embodiments 18-21, it can pass through the method for any one of embodiment 13-16 and obtain.
The method of any one of 23. embodiments 13-16, it also provides albumen, fat and carbohydrate to composition, To obtain the liquid nutritional compositions that protein concentration is 8 to 25g/100ml, described composition comprises based on total protein meter at least 30 The crosslinked micellar casein of weight %.
The composition of 24. embodiments 17-22 is used for improving the purposes of the heat endurance of liquid nutritional compositions.
The liquid enteral nutritional composition of 25. embodiments 1 or 2, it comprises:A) 9-20g albumen/100ml, preferably at least 11g albumen/100ml, wherein protein part comprise the micellar casein of crosslinking and at least one others albumen, described albumen portion Divide at least the 16% of the total energy content that composition is provided, and comprise the micellar casein of the crosslinking of at least 30 weight %;b) Fat, it provides at least 20%, preferably the 30% of the total energy content of composition;C) carbohydrate, it provides composition At least the 30% of total energy content, the energy density of described composition is at least 10kJ/ml [2.4kcal/ml].
The liquid enteral nutritional composition of 26. embodiments 25, it comprises to be less than the breast of 15 weight % based on total protein meter Clearly, it is preferably based on the lactalbumin that total protein meter is less than 10 weight %.
List of drawings
Fig. 1 show add and without 200mEq trisodium citrate (TSC) in the case of crosslinked micellar casein Size distribution.As comparison further it is shown that add and noncrosslinking micellar casein without trisodium citrate granularity Distribution.
Fig. 2 shows non-crosslinked (comparison) and crosslinked micella in the presence of 0,35 and 70mEq/L trisodium citrate (TSC) The viscosity of casein solution is with the change of shearing rate.
Fig. 3 show with uncrosslinked and crosslinked but compared with calcium and the nondecreasing MCI of phosphate, the friendship that calcium and phosphate reduce The setting time of the MCI of connection.Its display is when calcium and the reduction of phosphate (CCP) level in the product containing crosslinking micellar casein When, heat endurance dramatically increases.
Fig. 4 shows that albumen is to MgCl when the calcium in crosslinked micellar casein and phosphorus level reduce2Presence become Insensitive.Even if albumen would generally be made unstable and increase that is leading to viscosity and condensation a large amount of bivalent cations presence Under, the heat endurance of product is also maintained.
Specific embodiment
One preferred embodiment of the present invention is a kind of alimentation composition, its energy density is at least 1.0kcal/ml, More preferably at least 1.5kcal/ml, most preferably at least 2.0kcal/ml, and its protein content be at least 8g/100ml, more It is preferably 8 to 25g albumen/100ml, more preferably 9 to 25g albumen/100ml, more preferably 10 to 25g albumen/100ml, very To more preferably 12 to 25g albumen/100ml, most preferably 15 to 25g albumen/100ml, wherein albumen comprises based on total protein The crosslinked micellar casein of content meter at least 30 weight %, the crosslinked micellar casein of preferred 30-95 weight %, more preferably 35- The crosslinked micellar casein of 90 weight %, even more preferably 40 to 85 weight %, the crosslinked micella of most preferably 45 to 80 weight % Casein, based on total protein content meter.
In one embodiment, the present invention relates to a kind of alimentation composition, its energy density is at least 1.0kcal/ml, More preferably at least 1.5kcal/ml, most preferably at least 2.0kcal/ml, protein content is at least 8g/100ml, more preferably 8 to 25g Albumen/100ml, more preferably 9 to 25g albumen/100ml, more preferably 10 to 25g albumen/100ml, even more preferably 12 to 25g egg In vain/100ml, most preferably 15 to 25g albumen/100ml, wherein said albumen comprises based on total protein content meter at least 30 weight % Micellar casein, the micellar casein of preferred 30-95 weight %, the more preferably micellar casein of 35-90 weight %, even more Preferably 40 to 85 weight %, the micellar casein of most preferably 45 to 80 weight %, based on total protein content meter, wherein at least part Micellar casein is crosslinked.Preferably, at least 20 weight %, more preferably at least 40 weight %, even more desirably at least 60 weights Measure %, even more preferably still at least 80 weight %, the micellar casein of most preferably at least 90 weight % are crosslinked.
Preferably, using enzyme transglutaminase (TG), micellar casein is carried out with enzymatic crosslinking, but can also be suitable Other cross-linking enzymes are applied on ground, as long as realizing crosslinked in micella and controlling crosslinked between micella.Preferably crosslinked micellar casein It is the micellar casein of transglutamin-ase 9 ferment treatment, be abbreviated as " TGMC " throughout the specification.
In product, the crosslinking of micellar casein can be assessed by adding chelating agent such as sodium citrate or potassium citrate:? When adding calcium chelating agent such as sodium citrate or potassium citrate, the crosslinked size distribution of albumen micella and micella particle diameter will not be therefore Reduce, this is contrary with the non-crosslinked micellar casein leading to granularity to reduce due to sloughing of calcium.By measuring size distribution, can So that by crosslinked casein between micella, internally crosslinked casein distinguishes with micella.With cross-linked phase ratio in micella, crosslinking between micella To lead to bigger particle diameter skew.The internally crosslinked casein micelles of micella have with natural caseiBl micellar phase as particle diameter (average diameter about 200nm), and (much) is more than 200nm by crosslinked caseic granularity between micella.Below and embodiment Middle offer functional assays.
Micellar casein (MC) is the high-quality lactoprotein being present in cow's milk, and its concentration is about 2.6g/100ml.It leads to Cross and will not or be concentrated essentially without the method making casein denaturation, and as micellar casein isolate (MCI) sell.Micellar structure in breast is stabilized by calcium phosphate and is characterized with HMW.Casein micelles divide Seed footpath is equivalent to about 10000 casein monomers of each micella.It has intrinsic low viscosity property, therefore comprises micella junket The fluid composition of albumen is easily drunk.In addition to micellar casein, the non-micella junket that can be formed by such as sloughing of calcium Protein masses may result in less aggregation.Such protein sources still can be used for transglutamin-ase 9 ferment treatment, wherein divides Described aggregation is stablized in crosslinking in son effectively.Although not preferred, it is the micellar casein being crosslinked can comprise this The caseins aggregate body of decalcification.In a preferred embodiment, the term in the context of the invention " micellar casein " relates to And known in the art routine micellar casein.
By contrast, used in the context of the invention, caseinate refers to caseic form, and it has been out it Micellar structure is simultaneously sold as such as calcium caseinate, casein sodium and/or Caseins, potassium salts.Optionally, based on albumen Gross weight meter, described composition comprises the non-micella junket of 0-50 weight %, preferred 1-20 weight %, more preferably 5-10 weight % Albumen or caseinate or both.In one embodiment of the invention, casein or casein are casein sodium, junket Protein acid magnesium, Caseins, potassium salts, calcium caseinate or its any mixture.Also mixture such as Na/K- caseinate can be used With Na/Mg caseinate as caseinate source.In a preferred embodiment, described composition comprises junket Protein acid sodium or Caseins, potassium salts or both, preferably total amount is based on 0-50 weight % of albumen gross weight meter, more preferably 1-40 Weight %, even more preferably 5-30 weight %, most preferably 10 to 20 weight %.Preferably, do not use calcium caseinate or contain Ca Caseinate because micellar casein has been provided for enough calcium, thus should avoid adding unnecessary calcium.
As described above, the composition of the present invention should not contain a large amount of eggs in addition to micellar casein and caseinate In vain.In another embodiment of the present invention, based on total protein meter present in liquid nutritional compositions, described composition can Comprise to be up to about 30 weight %, preferred 1-20 weight %, more preferably less than 15 weight %, even more preferably less than 10 weight %, More preferably less than 7.5 weight % selected from whey and vegetable protein pea protein, soybean protein, potato protein, corn (maize) albumen and the albumen of wheat gluten.In another embodiment of the present invention, described composition can comprise presence Total protein in liquid nutritional compositions be up to about the whey of 30 weight %, the whey of preferred 1-20 weight %, more preferably Less than the whey of 15 weight %, the lactalbumin of more preferably less than 10 weight %, more preferably less than 7.5 weight % whey.
In the context of this application, the alimentation composition of the preferred pair present invention is heat-treated to extend its shelf life simultaneously Composition is made to be suitable for commercial use.It is therefore preferable that being heat-treated to the alimentation composition of the present invention, for example pasteurization or Sterilizing, to reduce micro- bacterial load.Typical pasteurization time is 30 seconds at 85 DEG C.Typical sterilization time is at 124 DEG C 4 Minute.If unclear from the above, in the case of optional heat treatment above such as heat sterilization, to glue in alimentation composition The sign restrainting caseic amount is applied to the composition before this heat treatment.Without being bound by theory, inventors believe that Due to crosslinking, casein micelles are less likely to occur the expansion that causes by mineral equilibrium change, described mineral equilibrium change be by Occur in heat treatment or shelf life.
Preferably, the energy density of composition be at least 1.8kcal/ml, more preferably at least 2.0kcal/ml, even more excellent Choosing at least 2.2kcal/ml, more preferably at least 2.3kcal/ml, even more desirably at least 2.4kcal/ml, and it is less than 4kcal/ Ml, preferably smaller than 3.5kcal/ml.Although composition has high-energy-density, it also has sufficiently low viscosity to allow It is likely difficult to swallow product or carries out those people of tube feed and absorb.Therefore, in one embodiment, described nutrient combination Thing is liquid, heat-killed product, and its measured viscosity under 20 DEG C with the shearing rate of 100/s is less than 500mPa.s, more excellent Choosing is less than 400mPa.s, more preferably less than 300mPa.s, even more preferably less than 200mPa.s, preferably 15 to 150mPa.s-1, excellent Select 15 to 100mPa.s-1.The rotary viscosity design determining viscosity of cone plate geometry can be used.
TGase (TG) (EC 2.3.2.13) can obtain from animal and two kinds of sources of microorganism.It is being applied to When in food system, more commonly using bacterium TG, for example by streptoverticillium (streptoverticillium S-8112, Streptoverticillium mobarense, streptoverticillium kind, draw Dacca streptomyces verticillatus (Streptoverticillium ladakanum), Streptoverticillium lydicus) a kind of TG of obtaining, because It has the degree that preferably can be utilized.Preferably use Activa YG (Ajinomoto Food Europe, France).The work of this enzyme Property is about 1000 units/g.
At present, outside the scope of the present invention, the TG in food is used for improving the quality in meat and ham production process, Wherein TG works as glue.In the protein solution of the present invention, TG can form two species with casein micelles when reacting The crosslinking of type:Crosslinked crosslinked and between micella in micella.Think that in micella, crosslinking internally fixes casein micelles, and hand between micella Connection will increase the viscosity of protein solution by gelling.Due to the more close degree of approach of albumen it is therefore contemplated that increase egg White concentration can stimulate intermicellar crosslinking.Even if however, the inventors discovered that a kind of albumen in rather high concentration and junket egg The crosslinked method more than crosslinking between micella in lower stimulation micella in vain.Result has surprisingly shown that 6 to 8, preferably 6 to 7.5, more Preferably 6.1 to 6.9, even more preferably 6.2 to 7.3, under most preferably 6.2 to 6.5 pH, TG hands in the micella of micellar casein Connection ratio crosslinking between micella is more favourable, even in the solution with high protein concentration.Therefore, caseic particle diameter is fixing , and protein concentration can be improved without having a negative impact to viscosity.More details are given in an embodiment.
The present inventors have additionally discovered that a kind of control (minimizing) is with the byproduct producing during using TGase relevant The method of problem.In multiple protein, there are three kinds by the reaction that TG is catalyzed, most important reaction is crosslinked.However, urging in TG It is also possible to occur amine to introduce and deamidation in the reaction changed.All three reaction all disadvantageously results in accessory substance ammonia (NH3) Produce.For cross-linking reaction, TG catalyzing acyl transfer reaction, the γ-carboxylic acyl of wherein protein bound glutaminyl residues Amine groups react as acry radical donor.At the carboxylacyl amine group of glutamine residue, enzyme exchanges multiple primary amine and ammonia.
As shown in Example 1 it may be determined that in TGase processing procedure release ammonia amount.The ammonia being discharged Amount with albumen introduce crosslinking quantity directly related, and therefore can be used for monitor TGase reaction.
Additionally, when protein bound lysine residue reacts as acyl acceptor, in protein bound glutamy Formed crosslinked between amine and lysine residue, and form ε-(gamma-glutamyl amine acyl group) lysine isopeptide bond.The journey of cross-linking reaction Depending on participating in the glutamine of reaction and the available degree of lysine, wherein said accessibility is subject to the structure of albumen to degree in turn again The impact of type, position and concentration.If taken no action to, the crosslinking of albumen can lead to undesired dimer, tripolymer and more The formation of big protein polymer.Expected this undesired effect increases with protein concentration, produces viscosity and unstable Product.
In consideration of it, the inventors discovered that preferably crosslinking is minimized to the degree needed for stable micellar casein solution, from And the formation of accessory substance is maintained at favourable low-level.In order that the available degree of glutamine and lysine reaches most preferably, Preferably the concentration carrying out the micellar casein of crosslinking is maintained at the micella junket egg of 7 to 15 weight %, preferably 8 to 10 weight % In vain, the gross weight meter based on the waterborne compositions carrying out crosslinking.As described above, it is preferred to by pending TGase ferment treatment The pH of the composition of limited amount micellar casein be adjusted to 6 to 8, or any preferred subrange.
Preferably micellar casein is cross-linked to such degree:Even if at least citrate of 70mEq/L is added to bag In solution containing crosslinked (' TG- is processed ') micellar casein, the particle diameter of casein micelles also will not significantly change (i.e., not Reduce).In the context of the present invention, (for example use less than the change of 10%, even more preferably less than 5% micella particle diameter Standardized Zetasizer technology measures) be still considered as acceptable.Therefore, comprise crosslinked micella junket in the present invention Albumen and optionally also comprise the composition of non-crosslinked micellar casein, those skilled in the art are it can be seen that add citric acid After salt, at least partly particle (micella) grain of (if there is non-crosslinked micellar casein) and preferably most of casein micelles Footpath distribution will not be to less particle/aggregate particle size skew, thus proving the micellar casein being present in product (at least Part) it is crosslinked.
Preferably, subsequently by enzyme-deactivating, for example, at least 5 minutes, preferably 65 to 110 DEG C are continued by being heated at least 65 DEG C Continue 10 seconds to 20 minutes.Real time depends on temperature, but enzyme activation is considered within the ken of technical staff.Go out The higher inactivation time typically requiring of temperature of living is shorter.Preferably, inactivation is entered at 65 to 85 DEG C, even more preferably 65 to 75 DEG C Row 20 seconds to 6 minutes.Preferably make crosslinked micellar casein and any other composition -- any other particularly optional egg Carry out enzyme activation before white material mixing.
Optionally, the caseic composition of crosslinked micella will be comprised be dried, and preferably pass through to be spray-dried, to obtain crosslinking Micellar casein, such as MCI (micellar casein isolate) powder of crosslinking.Described powder can be packed as former state and sell, or It is mixed for preparing the alimentation composition with high protein density with other nutrient contents.Therefore, one embodiment of the present invention The powder of the micellar casein (TGMC) that case is related to comprise the crosslinking of transglutamin-ase 9 ferment treatment, wherein crosslinked micellar casein In terms of the dry weight based on powder at least 30 weight %, preferably at least 40 weight %, more preferably at least 50 weight %, even more preferably 40-100 weight %, 50-95 weight %, most preferably 60 to 95 weight % and exist.In one embodiment, described powder is not Comprise any noncrosslinking micellar casein.In one embodiment, described powder comprises gross weight meter 90- based on powder The micellar casein of the crosslinking of 100 weight %.
Once above-mentioned preferably under the conditions of crosslinked, crosslinked micellar casein can be used for the fluid composition of the present invention In.In order to obtain liquid low viscosity high protein and the high heat composition of the present invention, can carry in crosslinked micellar casein For fat and carbohydrate and other optional albumen and mineral matter, the protein concentration of liquid nutritional compositions is preferably made to reach To the preferred subrange of 8 to 25g/100ml or any, described composition comprises the micella junket based on total protein meter at least 30 weight % Albumen, the micellar casein of preferably at least 50 weight %, the micellar casein of more preferably at least 70 weight %, most preferably at least 90 The micellar casein of weight %, based on total protein meter, wherein at least part micellar casein is crosslinked.Preferably real at one Apply in scheme, in crosslinked micellar casein, provide fat and carbohydrate and other optional albumen and mineral matter, So that the protein concentration of liquid nutritional compositions is the preferred subrange of 8-25g/100ml or any, described composition comprises base Micellar casein in the crosslinking of total protein meter at least 30 weight %.Other albumen can include casein and caseinate, One or more of lactalbumin.
Preferably, in the composition, crosslinked micellar casein is at least with respect to the relative quantity of total protein content 30%, more preferably at least 35%, 40%, 45%, 50%, 55% or 60%, even more desirably at least 75%, preferably up to reach 100%, even more preferably at most reach 95%.If using more than one protein sources in alimentation composition, preferably in glue These protein sources are mixed after having carried out crosslinking by bundle Casein in Milk.In one embodiment, in addition to TGMC, combination Albumen in thing also comprise micellar casein (non-TG- process) or caseinate or both.
The protein sources comprising can be used for the micellar casein of TG cross-linking reaction include micellar casein isolate (MCI), example As obtained from Ingredia;Milk protein isolate (MPI), it comprises the micellar casein of total protein content about 80%;Breast Protein concentrate (MPC), it generally passes through ultrafiltration (ultrafiltration breast, UF breast) and prepares, and it also contains based on total protein content meter about 80% micellar casein;Skimmed milk (defatted milk) and fresh or pasteurization dairy products.Any breast can be used in principle Source, such as cow's milk, goat dairy, sheep breast etc..Preferably use cow's milk, because this source generally can preferably be obtained on an industrial scale ?.These micellar casein sources can be used in combination with any micellar casein source or with selected from following any source:Plant Protein sources, such as soybean protein, pea protein and potato protein, or the hydrolysate of all plant protein sources referring to;Or breast egg Bai Yuan, such as caseinate, lactalbumin or its hydrolysate.
Micronutrient
The micronutrient of untreated micellar casein is somewhat restricted due to the unstability of micellar casein. Calcium ion in micellar casein can be exchanged because of the change of the pH of total composition or ionic strength.Normal micellar casein Contain about 800-3400mg calcium/100g powder (i.e. the calcium of 0.8-3.4 weight %, based on protein content meter).Discovery comprises crosslinking The calcium content of the composition of micellar casein can be reduced to extremely low level, unstable without making micellar casein, Or originally the low viscosity of composition can be adversely affected.Based on total protein content meter, calcium content is preferably smaller than 2.2 weights Amount %, more preferably less than 2.0 weight %, even more preferably less than 1.75 weight %, more preferably less than 1.55 weight %, particularly Calcium less than 0.7 weight %, especially less than 0.3 weight %.
One embodiment of the invention is related to a kind of powder, and it comprises gross weight meter at least 30 weight based on composition The micellar casein (TGMC) of transglutamin-ase 9 ferment treatment of amount % and the calcium being less than 0.8 weight % based on total protein content meter, It is preferably based on the calcium that total protein content meter is less than 0.7,0.6,0.5,0.4,0.3 or 0.2 weight %.
When needing high protein concentration (higher than 10g/100ml), low calcium level is especially relevant;In this case, calcium water The flat level that can be easily increased to above-mentioned recommendation:175mg/100kcal (food [FSMP] the EC directive/guide of special medical purpose) With 80mg/100kcal (NIMS).In a preferred embodiment of the invention, described composition therefore comprises based on albumen Gross weight meter is less than the calcium level of 0.4 weight %, the calcium of preferably smaller than 0.2 weight %, even more preferably less than 0.1 weight %, Total protein content meter based on composition.For energy content, the calcium that preferably described composition comprises to meet above-mentioned recommendation is dense Degree, i.e. preferably shorter than 175mg/100kcal, more preferably less than 80mg/100kcal.Can be produced using crosslinking technological have super Cross 9g albumen/100ml, more preferably above 10g/100ml albumen, most preferably more than 12g/100ml albumen and less than 90mg calcium/ The product of 100ml, and do not damage the characteristics of liquids of product.This is impossible when using intact proteins.
Similarly, the phosphate concn in micellar casein is the reason in protein composition, phosphorus level sharply increases.? In one preferred embodiment, phosphorus level in the albumen gross weight meter based on albumen is less than 1.55 weight %, preferably shorter than 0.25 weight %, more preferably less than 0.2 weight % and most preferably less than 0.1 weight %, the gross weight meter based on albumen.
A kind of preferred composition of the present invention is the fluid product containing micellar casein, and wherein calcium level is less than 0.4 weight Amount %, phosphate level is less than 0.25 weight %, the total protein content meter based on composition.
A kind of appropriate method for minimizing phosphate and calcium from micellar casein will comprise the following steps:
1. pH is acidified to for 6.6 to 5.0, preferably 6.2 to 5.5 using such as citrate, lactate, EDTA, HCl, with Dissolving is present in the colloidal calcium phosphate nanocluster in the casein micelles of crosslinking;
2. filtered after by micellar casein crosslinking.By filtering, comprise the albumen of the micellar casein of TG process Phosphate level in partly and calcium level can be reduced to desired low-level.Any suitable filter method, example can be used As ultrafiltration, micro-filtration, nanofiltration, diafiltration or a combination thereof.Preferably, ultrafiltration is used in combination with diafiltration.
3. pH 6.5 to 7.5 is neutralized to using alkaline solution such as NaOH or KOH.
Method for reducing phosphate and calcium preferably includes dialysis step in addition to filtration step or is replaced with dialysis step For filtration step.Any dialysis process generally known to those skilled in the art will be all suitable, preferably electrodialysis.At one In preferred embodiment, bivalent cation calcium and phosphate can be reduced using ion exchange.
Thus obtained solution can be evaporated step desired needed for being spray-dried to be concentrated into protein solution Dry matter content.
A kind of preferred alimentation composition of the present invention comprises at least 150kcal/100ml, at least 9g albumen/100ml and little In 80mg calcium/100kcal, more preferably at least 150kcal/100ml, at least 10g albumen/100ml and less than 80mg calcium/ The finished product of 100kcal, and most preferably at least 200kcal/100ml, at least 12g albumen and less than 80mg calcium/100kcal Alimentation composition.The amount of the micellar casein of the crosslinking that described alimentation composition is comprised is based on total protein content meter preferably extremely Few 30 weight %, more preferably at least 50 weight %, wherein other albumen be selected from casein and caseinate (sodium and/or potassium), Whey, soybean and pea protein.
Digestible carbohydrate
In one embodiment of the invention, the liquid nutritional compositions of the present invention also comprise digestible carbon hydrate Thing, described digestible carbohydrate provides the 30 to 60% of the total energy content of composition.For 2.0kcal/ml combination For thing, this is equivalent to 80 to 120kcal/100ml.Preferably, digestible carbohydrate provides the composition of the present invention Total energy content at least 40%.Described digestible carbohydrate may include simple or compound carbohydrate, Or its any mixture.Be suitable for the present invention is glucose, fructose, sucrose, lactose, trehalose, palatinose, primverose Slurry, malt, maltose, isomaltose, the cornstarch of partial hydrolysis, maltodextrin, gluco-oligosaccharides and glucose are many Sugar.
Because the present invention relates to having the product of hyperpyrexia metric density, the concentration of carbohydrate is relatively high and preferably should be selected from Polysaccharide, because these carbohydrate are minimum to the infiltrative contribution of liquid nutritional compositions.A reality in the present invention Apply in scheme, described digestible carbohydrate includes having the maltose (maltodextrose) of high DE, and (dextrose is worked as Amount).In one embodiment, described digestible carbohydrate includes the malt dextrose of DE > 15, preferred > 20.
The use of maltose leads to the little or no maillard reaction product in heating.Do not restrainted by any explanation Tie up, now think that this effect is attributable to following facts:The closely knit micellar structure of micellar casein is hardly provided for Mei Lade The lysine reaction site of reaction.In one embodiment of the invention, described digestible carbohydrate includes having The maltose of high DE, its content is at least 35 weight % of the gross weight of digestible carbohydrate, preferably at least 50 weights Amount %, preferably at least 65 weight %, preferably at least 90 weight %.
In another embodiment of the present invention, described digestible carbohydrate includes trehalose.As described above, One of main object of the present invention is to provide one kind to have low viscous alimentation composition.Sucrose is highly suitable for this purpose, But lead to the very sweet composition that consumer does not generally like.Have low DE (e.g., from about 2) maltose do not have after Shortcoming, but lead to high viscosity.The maltose with high DE (e.g., from about 47) leads to low viscosity, but very sweet, and also leads Cause undesirable Maillard reaction.Trehalose is one of indigestible carbohydrate and preferably selects, because it leads to low gluing Spend, undesirable Maillard reaction does not occur and its sugariness is about the half of sucrose.In one embodiment of the invention, institute State digestible carbohydrate to comprise content is the trehalose to 60 weight % for 20 weight %.
Method for preparing the internally crosslinked micellar casein of TGase micella (TGMC)
In one aspect of the invention, the method for preparing the nutrition product of the present invention includes preparing micellar casein The step of solution, the concentration of described micellar casein solution is 7 to 15g micellar casein/100ml, preferably 8 to 12g/100ml, Even more preferably 9 to 11g/100ml.Preferably pH is adjusted and is maintained at 6 to 8, preferably 6.0 to 7.5, more preferably 6.1 to 6.9, Even more preferably 6.2 to 7.3, preferably 6.2 to 6.8 level.Little micella particle diameter is obtained under 6.2 to 6.8 pH.With pH mono- Rise, protein concentration within the above range is to control one of crosslinked parameter so that primarily forming crosslinked, more than micella in micella Between crosslinked or crosslinked no between micella.Preferably whey portion is removed by the filtration of lactoprotein according to standard method known in the art Divide and to prepare micellar casein solution.Advantage of this is that casein in the solution can be directly used for and turns glutamy The cross-linking reaction of amine enzyme, and need not any aforementioned treatment Step.
Subsequently use standard incubation technology to adopt TG enzyme to be incubated protein solution, preferably the final concentration of 5-100 unit of TG enzyme/ G albumen, preferably 10 to 75 units/g albumen, even more preferably 15 to 25 units/g albumen, and optimization protein concentration is 7 to 15g/ 100ml, preferably 8 to 12g/100ml, even more preferably 9 to 11g/100ml.This concentration is crosslinked in formation micella to be more than glue It is important in the crosslinked management and control of interfascicular.Incubation is preferably at 30 to 55 DEG C, more preferably 35 to 50 DEG C, even more preferably 40 to 50 DEG C At a temperature of carry out.Optimum temperature is 44 to 46 DEG C.Incubation time is relative to each other with temperature.Temperature is lower, obtains satisfactory The crosslinked incubation time needing of level is longer.Under 30 to 55 DEG C of incubation temperature, incubation time is preferably 6 to 1 hours.? At a temperature of 40 to 50 DEG C, incubation time is preferably 2.5 to 3.5 hours.Anyway, incubation time and temperature are technical staff Parameter in ken.
After incubation, optionally enzyme is inactivated, and can easily will be dense for the composition containing crosslinking micellar casein Contract or be dried for using further, as described above, that is,:Fluid composition for the present invention for comprising a large amount of albumen provides Heat endurance.
The alimentation composition of the present invention preferably comprises albumen, fat and carbohydrate, and wherein protein content is 8 to 25 weights Amount %, and comprise the TGMC of total protein content meter 30-95 weight % based on composition, fat content is total based on composition Weight meter 6-25 weight %, the content of digestible carbohydrate is gross weight meter 1-60 weight % based on composition, and Wherein energy density is 1.5 to 4.0kcal/ml.
Embodiment 1:TG processes the impact to micellar casein particle diameter, viscosity and stability
Sample preparation
It protein content is the micellar casein of lactalbumin for 82% (w/w%) wherein about 5% (w/w%) Separator (MCI) protein powder (In gredia, France) is dissolved in warm water (± 70 DEG C) so that protein concentration is about 10% (w/w), and using laboratory stirrer (RW20.n, IKA Labortechnik, Staufen, Germany) stir at 600 rpm 15 minutes.Then, protein solution is made to be homogenized under the pressure of 350/50bar (NS2006L, GEA Niro Soari S.P.A., Parma, Italy).Using the Mastersizer2000 equipment (Malvern comprising the water-bath of waterpower 2000G Instruments, Worcestershire, Britain) measure the granularity of described protein solution it is ensured that obtaining diameter D [4,3] is about 0.15 μm of single casein micelles.After homogenizing, the pH of MCI solution is about 6.6-6.7, and temperature is about 40 DEG C.
TGase (Activa YG, Ajinomoto Food Europe, France) is dissolved in demineralized water So that concentration is 5% (w/w).Solution is stirred 2 hours, to guarantee that described enzyme is completely dissolved.Volume is turned paddy ammonia for 10ml Acid amides enzyme solutions are added in 180ml MCI solution, are subsequently incubated 3 hours in the water-bath at 45 DEG C, apply constant simultaneously Stirring.Enzyme inactivation carries out 10 minutes at 70 DEG C in a water bath, is then cooled to room by being immersed in solution in cold bath Temperature.Noncrosslinking (comparison) MCI solution is by being added to 180ml MCI by 10ml demineralized water rather than Activa YG solution To prepare in solution.
Subsequently, (crosslinking) the MCI solution of transglutamin-ase 9 ferment treatment and comparison (noncrosslinking) MCI solution are divided into The volume of 95ml.In order to measure the crosslinking degree of casein micelles in MCI solution, to one of described solution middle addition 5ml lemon Sour trisodium (TSC) (4000mEq.L-1) so that in MCI solution TSC final concentration of 200mEq.L-1, simultaneously by 5ml demineralized water (demiwater) it is added in other MCI solution as reference.Also in crosslinked MCI solution and comparison MCI solution, add one Determine concentration (0,35 and 70mEq.L-1TSC TSC).Now, the protein concentration of every kind of solution be 9% (w/w), and by pH adjust to 6.6±0.05.Protein solution is gently mixed at room temperature about 17 hours so that solution reaches balance.If sent out during storing Raw deviation, then carry out the regulation of final pH.PH deviation is always little and sample does not show any visible corruption.
Size distribution
Survey by using Zetasizer Nano ZS (Malvern Instruments, Worcestershire, Britain) The size distribution of amount protein solution with determine transglutamin-ase 9 enzyme crosslinking after adding trisodium citrate (TSC) to casein micelles The impact of integrality.Protein solution is diluted 100 times in demineralized water, is filtered with 0.8 μm of injection filter, and at 25 DEG C Measurement in disposable particle diameter sample cell (sizing cuvettes) (DTS0012 type).Protein solution is balanced 120 seconds, and Measured using back scattering at 90 DEG C.Refractive index for casein micelles is 1.57, and the refractive index for continuous phase is 1.33 (water).Each measurement parallel carries out three times.Obtain the percent by volume of Z- mean value and size distribution.Result is shown in Figure 1.
Viscosity
Cup and hammer solid are used using MCR 300 flow graph (Anton Paar Physica, Graz, Austria) (CC27 graduated cylinder) measures the viscosity of protein solution at 20 DEG C.Viscosity is in 1-1000s-1Shearing rate under measure.Each measurement is flat Row is carried out three times, and the viscosity being measured is represented with mPa.s.Result is shown in Figure 2.
Ammonia density
Measure kit (catalog number (Cat.No.) AA0100, Sigma-Aldrich Co.LLC, USA) mensure ammonia by using ammonia dense Degree.Using demineralized water by 10 times of Sample Dilution, and the sample of 100 μ l volumes and 1.0ml ammonia are measured reagent in cuvette Mixing.Prepare blank by using 100 μ l demineralized waters, and by using measuring 50 μ l ammonia in reagent in 1.0ml ammonia (ammonia density is about 10 μ g.ml to standard liquid-1) and prepare standard items.All mixtures are incubated about 30 minutes at room temperature, and The absorbance (initial A) of every kind of mixture is measured under 340nm.Subsequently, 10 μ l Pidolidones are added in each cuvette Mixture is simultaneously incubated 5 minutes by dehydrogenase solution.Then, measure the absorbance (final A) of every kind of mixture under 340nm. Calculate ammonia density (mg NH using equation below3/ ml initial sample volume).
The final A of the initial A- of Δ A340=
Δ (Δ A340) sample or standard items=Δ A340 (trial target or standard items)-Δ A340 (blank)
·mg NH3/ mL=[A × TV × MWNH3×F]/[ε×d×SV×1000]
=[A × TV × F]/[SV × 0.00273]
Wherein
A=Δ (Δ 340), the absorbance of sample or standard items
TV=always measures volume (ml)
SV=sample volume (ml)
The MW=17g.mol of ammonia-1
F=is derived from the dilution gfactor of sample preparation
Extinction coefficient=6.22mM at 340nm for the ε=NADPH-1cm-1
D=cuvette light path (cm)=1cm
Result
Fig. 1 illustrates to add trisodium citrate (TSC) to lead to granularity to reduce in noncrosslinking MCI, is most likely to be by junket The disintegration of albumen micella causes.The method according to the invention, after using transglutamin-ase 9 ferment treatment, the crosslinked junket egg of gained The particle diameter distribution of white glue bundle is not added by TSC to be affected.
After Fig. 2 illustrates to add trisodium citrate (TSC) in noncrosslinking casein micelles, the micella of disintegration is than complete Crosslinked micella combines more water, leads to the viscosity of composition to increase.
Also find, compared with the similar liquids emulsion (comparison) comprising noncrosslinking casein micelles (about 22 minutes), need To make liquid emulsion (25 minutes) thermal coagulation comprising casein micella the more time.These changes are considered as important , particularly when recognizing that bulk sterile generally carries out about 20 minutes at 120 DEG C in the art.Therefore, crosslinked improvement The heat endurance of the micellar casein solution of embodiment 1.
After removing calcium from crosslinked albumen and phosphate, heat endurance is further enhanced (Fig. 3).Calcium concentration drops As little as based on the total solids in protein solution about 2.01 weight %, and phosphate concn is reduced to based on total in protein solution Solid meter about 1.29%.The phosphate of these low amounts and calcium lead to the thermal coagulation time to increase to above 50 minutes from about 10 minutes. In addition, when comparing micellar casein isolate (MCI) of crosslinking of calcium and phosphate minimizing, the impact of bivalent cation It is significantly reduced.Other details provide in the following Example 3.
Embodiment 2:Product embodiments
Table 1 give containing different amounts of TG process micellar casein sterilizing high protein composition (1)-(7) and The representative of its viscosity.
Embodiment 3:The removing of Ca and P
Method:Powder is dissolved into 10% albumen, homogeneity under 350 ± 50bar.Demineraliting is added in 90ml sample Water (Fig. 3) or 5ml 200mEq/L MgCl2Solution (Fig. 4).By adding 0.5N HCl and/or 0.5N NaOH by all solution PH adjust to 6.6 (Fig. 3) or 6.8 (Fig. 4).Add demineralized water so that the cumulative volume of each sample reaches 100ml.
Sample is put in the screw-topped glass tube of tool, and heats in 126 DEG C of oil bath.To observable in the sample Time to aggregation is recorded as the thermal coagulation time.Often tilt sample to help observe.After oil bath is heated 50 minutes, stop Only observe.
When the calcium in crosslinked micellar casein isolate and phosphate reduce, the thermal coagulation time dramatically increases.? MgCl2In the presence of (being also the standing model of other bivalent cations), if removing calcium and phosphate from crosslinked MCI (CCP), then the thermal coagulation time (HCT) increases.

Claims (25)

1. the protein-contg fluid composition of a kind of bag, wherein protein concentration are 11 to 25g/100ml, and described composition comprises crosslinking Micellar casein, wherein preferably by heat sterilization or pasteurization, described composition is heat-treated.
2. the protein-contg fluid composition of a kind of bag, wherein protein concentration are 11 to 25g/100ml, and described composition comprises crosslinking Micellar casein, wherein said albumen comprises at least 30 weight %, preferably at least 50 weight %, more preferably at least 70 weights Amount %, the micellar casein of most preferably at least 85 weight %, and wherein said albumen is from micellar casein isolate (MCI) Protein sources obtain, and based on total protein meter, wherein at least part micellar casein is crosslinked and wherein preferably passes through heating Sterilizing or pasteurization are heat-treated to described composition.
3. fluid composition in any one of the preceding claims wherein, also comprises fatty and digestible carbohydrate, and And wherein said albumen comprises the micellar casein of the crosslinking based on total protein meter at least 30 weight %.
4. fluid composition in any one of the preceding claims wherein, wherein said albumen comprises the friendship of 35 to 100 weight % The micellar casein of connection.
5. fluid composition in any one of the preceding claims wherein, the energy density of wherein said composition is at least 1.0kcal/ml, preferably at least 1.5kcal/ml and even more preferably 2.0 to 3.0kcal.
6. fluid composition in any one of the preceding claims wherein, is wherein based on total protein content meter, and calcium concentration is less than 2.6 Weight %, preferably shorter than 1.5 weight %, preferably shorter than 0.4 weight %.
7. fluid composition in any one of the preceding claims wherein, wherein said composition is at 20 DEG C and 100s-1Shearing Under rate, measured viscosity is 5mPa.s to 500mPa.s, preferably 5 to 200mPa.s.
8. fluid composition in any one of the preceding claims wherein, wherein said composition also comprises casein sodium, junket Protein acid calcium, magnesium caseinate or Caseins, potassium salts, or its mixture, preferably casein sodium or Caseins, potassium salts or both.
9. fluid composition in any one of the preceding claims wherein, it also comprises at least one vegetable protein, preferably at least A kind of vegetable protein selected from pea protein, soybean protein, wheat gluten, potato protein and zein.
10. fluid composition in any one of the preceding claims wherein, it comprises the gross weight meter based on albumen in composition Less than 1.6 weight %, preferably smaller than 1.3 weight %, more preferably less than 0.25 weight % phosphorus.
11. fluid compositions in any one of the preceding claims wherein, it comprises at least 11, preferably at least 12g/100ml Albumen, even more preferably 12 to 20g albumen/100ml.
A kind of 12. methods preparing the composition of micellar casein comprising crosslinking, it includes:A () provides a kind of pH is 6 to 8 Fluid composition, it comprises gross weight meter 7 to 15 weight % based on composition, the micella junket egg of preferably 8 to 10 weight % In vain;B () carries out transglutamin-ase 9 ferment treatment to described composition, preferably at a temperature of 37 to 50 DEG C, preferably at about 45 DEG C, To obtain the composition of the micellar casein comprising crosslinking;(c) optionally pH is adjusted to higher than 6.6 and/or to composition Carry out enzyme inactivation, and wherein described in preferred pair, composition carries out heat sterilization or pasteurization, preferred heat sterilization.
13. methods according to claim 12, the wherein combination to the micellar casein comprising crosslinking obtaining in (b) Thing is filtered, and wherein filter after, preferred pair composition carries out dialysis.
14. methods according to claim 12 or 13, wherein said transglutamin-ase 9 ferment treatment includes making composition in institute At a temperature of stating with least 0.05 weight %, preferred 0.1-0.55 weight %, more preferably 0.1-0.35 weight % transglutamin-ase 9 Enzyme contacts preferably at least 1 hour, 0.5 to 24 hour, preferably 1 to 5 hour, more preferably 2 to 4 hours.
Described crosslinked micellar casein composition is wherein done by 15. methods according to any one of claim 12-14 Dry to form powder, it is preferred to use spray drying process.
A kind of 16. compositions of the micellar casein comprising crosslinking, it can be obtained by the method for any one of claim 12-15 ?.
A kind of 17. powder compositions, it comprises the micellar casein of the crosslinking of gross weight meter at least 30 weight % based on powder.
18. powder according to claim 17, it comprises the glue of the crosslinking based on powder gross weight meter 90-100 weight % Bundle casein.
19. powder according to claim 17 or 18, it comprises to be less than the calcium of 0.8 weight % based on total protein content meter.
20. powder according to claim 17-19, it comprises phosphorus less than 1.4 weight %, preferably smaller than 0.4 weight % Phosphorus.
21. powder according to claim 17-20, it can pass through the method for any one of claim 12-15 and obtain.
22. methods according to any one of claim 12-15, it also provides albumen, fat and carbon aquation to composition Compound, to obtain the liquid nutritional compositions that protein concentration is 8 to 25g/100ml, described composition comprises based on total protein meter The micellar casein of the crosslinking of at least 30 weight %.
23. compositions according to claim 16-21 are used for improving the purposes of the heat endurance of liquid nutritional compositions.
24. liquid enteral nutritional composition according to claim 1 and 2, it comprises:A) 9-20g, preferably at least 11g egg In vain/100ml, wherein said protein part comprises the micellar casein of crosslinking and other albumen at least one, described protein part At least the 16% of the total energy content of offer composition, and comprise the micellar casein of the crosslinking of at least 30 weight %;B) fat Fat, it provides at least 20%, preferably the 30% of the total energy content of composition;C) carbohydrate, it provides the total of composition At least the 30% of energy content, the energy density of described composition is at least 10kJ/ml [2.4kcal/ml].
25. liquid enteral nutritional composition according to claim 24, it comprises to be less than 15 weight % based on total protein meter Whey.
CN201580028792.6A 2014-04-11 2015-04-09 Stabilized micellar casein and compositions Pending CN106455640A (en)

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