Classifications

• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
  • A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
  • A23L33/20—Reducing nutritive value; Dietetic products with reduced nutritive value
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23C—DAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING OR TREATMENT THEREOF
  • A23C19/00—Cheese; Cheese preparations; Making thereof
  • A23C19/06—Treating cheese curd after whey separation; Products obtained thereby
  • A23C19/068—Particular types of cheese
  • A23C19/08—Process cheese preparations; Making thereof, e.g. melting, emulsifying, sterilizing
  • A23C19/082—Adding substances to the curd before or during melting; Melting salts
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23C—DAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING OR TREATMENT THEREOF
  • A23C9/00—Milk preparations; Milk powder or milk powder preparations
  • A23C9/12—Fermented milk preparations; Treatment using microorganisms or enzymes
  • A23C9/13—Fermented milk preparations; Treatment using microorganisms or enzymes using additives
  • A23C9/137—Thickening substances
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
  • A23G3/00—Sweetmeats; Confectionery; Marzipan; Coated or filled products
  • A23G3/34—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof
  • A23G3/346—Finished or semi-finished products in the form of powders, paste or liquids
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23J—PROTEIN COMPOSITIONS FOR FOODSTUFFS; WORKING-UP PROTEINS FOR FOODSTUFFS; PHOSPHATIDE COMPOSITIONS FOR FOODSTUFFS
  • A23J3/00—Working-up of proteins for foodstuffs
  • A23J3/04—Animal proteins
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
  • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
  • A23L27/60—Salad dressings; Mayonnaise; Ketchup
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
  • A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
  • A23L29/20—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
  • A23L29/275—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of animal origin, e.g. chitin
  • A23L29/281—Proteins, e.g. gelatin or collagen
  • A23L29/284—Gelatin; Collagen
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
  • A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
  • A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
  • A23L33/17—Amino acids, peptides or proteins
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
  • A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
  • A23L33/20—Reducing nutritive value; Dietetic products with reduced nutritive value
  • A23L33/21—Addition of substantially indigestible substances, e.g. dietary fibres
  • A23L33/28—Substances of animal origin, e.g. gelatin or collagen
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K38/00—Medicinal preparations containing peptides
  • A61K38/16—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
  • A61K38/17—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans
  • A61K38/39—Connective tissue peptides, e.g. collagen, elastin, laminin, fibronectin, vitronectin, cold insoluble globulin [CIG]
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
  • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

• the present invention relates to particles of collagen material, which are used in particular in the production of food, and a process for their preparation.
• the invention further relates to compositions comprising such particles.
• fat substitutes such as starch, cellulose, modified cellulose, dextrins, carrageenan, xanthan and guar have been described as fat substitutes.
• An example of this is the fat substitute described in US 5,294,457, which comprises hydrolyzed cereal fibers, carrageenan and / or xanthan gum.
• proteins both vegetable and animal raw materials are used.
• WO 2006/058538 A1 describes a process for the production of microparticulate protein, in particular based on wheat protein.
• WO 2006/076051 discloses aqueous protein dispersions starting from soybean, milk and egg proteins.
• EP 0 241 896 B1 describes a water-binding and gelling agent which is prepared by drying and grinding defatted pork rind.
• the present invention has for its object to propose a suitable as a fat substitute in food product, which is simple and inexpensive to produce and nutritionally harmless, and with which the typical texture of fatty food can be simulated as well as possible. Another object is to propose a method of making this product.
• particles of collagen material which are substantially insoluble in water but swellable, the particles having a mean diameter of less than about 150 ⁇ m in the swollen state.
• Collagen is an insoluble fibrous protein of vertebrates and is the major component of connective tissue fibers and bone.
• a collagen material is to be understood as meaning a material which is formed predominantly of collagen.
• the material may consist essentially entirely of collagen.
• An essential property of the particles according to the invention is that they are substantially insoluble in water and are present in the form of a dispersion.
• the particles due to the hydrophilic structure of the collagen, the particles have a high swelling capacity and can therefore absorb and bind relatively large amounts of water.
• the fat content in food can be quite or be partially replaced by collagen or water, resulting in a significant reduction of the energy content.
• the inventors have found that the desired effect of a creamy texture with the particles of collagen material according to the invention can already be achieved in a swollen state from an average diameter of less than about 150 ⁇ m.
• the average diameter is preferably about 20 ⁇ m to about 100 ⁇ m, more preferably about 40 ⁇ m to about 80 ⁇ m.
• Wheat protein are according to the prior art z.T. significantly smaller particle diameter required.
• the corresponding particle diameters in the dry state are significantly smaller, generally about 5 to 10 times.
• Crucial, however, are the properties of the swollen particles as they are in the food.
• the particles of the present invention are substantially water-insoluble even at elevated temperatures, unlike, for example, gelatin obtained by extraction of collagen-containing materials and which form gel structures at lower temperatures which gradually dissolve upon heating.
• a further advantage of the particles according to the invention is thus that due to the insolubility of the collagen material, the viscosity or pasty consistency of a corresponding dispersion is maintained even at relatively high temperatures. This high hot viscosity makes you one Use of the particles according to the invention also in such foods possible, which are prepared hot and / or hot and / or consumed.
• the particles according to the invention preferably have a polydispersity index of at least about 0.3, more preferably of at least about 0.5.
• the polydispersity index is a measure of the scattering of the particle size, the index assuming the theoretical maximum value of 1, if all particles have the same diameter.
• the collagenous material of the particles of the invention is derived from vertebrate bone.
• the use of collagen from bone has several advantages over the use of skin tissue collagen (e.g., cattle split or pigskin).
• skin tissue collagen e.g., cattle split or pigskin.
• the inventors have found that particles in the desired order of magnitude can be produced more easily from bone collagen than from skin collagen, since in the latter case rather fibrous structures are obtained. This effect is probably due to different cross-linking structures of the collagen molecules in bone or in skin tissue.
• bone collagen that are substantially tasteless and odorless than corresponding products from cattle split or, in particular, pork rinds.
• the latter are used only in meat or sausage products because of their own taste, while largely taste-neutral particles from bone collagen are also used in other areas, e.g. for cheese imitations, dressings or desserts.
• the collagen material is derived from mammals, particularly pigs, cattle, sheep or goats, as well as from poultry or fish.
• bone derived collagen material it preferably comprises ossein. This is degreased and demineralized bone material, which is also used to make gelatine.
• the collagen material preferably has a fat content of less than about 5 wt .-%, in particular less than about 2 wt .-%, each based on the dry matter.
• the particles of the invention can thus also be used for the preparation of substantially fat-free foods.
• the low fat content also contributes to the odor and taste neutrality of the particles according to the invention, since the odor problem is often caused by oxidation of fat during the manufacturing process.
• a further aspect of the present invention relates to a composition, in particular for the production of foods, which comprises the particles according to the invention and a substantially water-soluble material, wherein the particles are dispersed in a matrix of the water-soluble material.
• composition has the advantageous effect that dried particles according to the invention, when they come into contact again with an aqueous medium during food production, can be redispersed very well.
• aggregates can form without the addition of a soluble matrix material, which are very difficult to redispersed.
• the composition according to the invention can be present both in dried form, the water-soluble material acting as a kind of release agent, and in a hydrated state in which the carbonate gene particles are swollen, and the water-soluble material in the form of a true solution, a colloidal solution or a gel is present.
• the water-soluble material can be calorific usable, but it can also be a soluble fiber.
• Preferred water-soluble materials are selected from gelatin, collagen hydrolyzate, modified starch, dextrins, locust bean gum, guar, konjac, tare, gum arabic, modified cellulose, and mixtures thereof.
• the water-soluble material preferably has a high cold water solubility.
• the proportion of the water-soluble material in the composition is preferably in the range of about 15 to about 75 wt .-%, based on the dry matter.
• the proportion required to achieve the desired effect will generally depend on the nature of the water-soluble material, which selection in turn will be influenced by the particular application or type of food.
• this in addition to the collagen particles, further comprises one or more insoluble fibers and / or insoluble proteins.
• the dietary fibers and / or proteins are preferably present as particles of the same order of magnitude as the particles of collagen material. To do so these components also contribute to the desired creamy texture of the food by mimicking the mouthfeel caused by emulsified fat droplets.
• Preferred insoluble fibers are selected from cellulose and / or hemicellulose-containing substances.
• An example of a suitable fiber is wheat fibers.
• Insoluble proteins which can be used in the composition according to the invention are preferably selected from zein, casein and / or soy protein. In order to make the proteins insoluble, they can be crosslinked, in particular by means of transglutaminase.
• the object underlying the invention is achieved in that the method for producing the particles of collagen material according to the invention comprises the following steps:
• comminuting the collagen material in an aqueous slurry is a particularly suitable method for producing particles of collagen material in the size range of the invention, ie, particles having an average diameter of less than about 150 ⁇ m.
• particles having an average diameter of about 20 ⁇ m to about 100 ⁇ m are obtained, more preferably from about 40 ⁇ m to about 80 ⁇ m.
• the particles are already present during comminution in the swollen state to which the size data relate.
• the collagen material used in step a) preferably comprises ossein, which is made by degreasing and demineralizing bone.
• ossein which is made by degreasing and demineralizing bone.
• the aqueous slurry is preferably prepared by slurrying coarsely crushed collagen material having an average particle size of about 2 mm or less in an aqueous medium. This coarse comminution is to ensure that the aqueous slurry has sufficient flowability for further processing. For coarse comminution, conventional methods such as e.g. Wolfen are used.
• the weight ratio of the collagen material to the aqueous medium in the preparation of the slurry is preferably in the range of about 1:10 to about 1: 0.25.
• the decisive factor in choosing this ratio is that there is sufficient flowability of the slurry for the subsequent mechanical comminution.
• the mechanical comminution of the collagen material in step b) preferably comprises high-pressure homogenization.
• high-pressure homogenization which also for Homogenizing the fat content in milk is applied, there is a reduction of the particle size of the collagen material by shear, impact and primarily cavitation forces.
• the pressures used in this case can be in the range of about 1000 bar, for example.
• Another preferred method which can be used alternatively or additionally in step b), is a wet milling of the collagen material, for example by a colloid mill.
• a procedure has proven particularly advantageous in which the collagen material in the slurry is first subjected to wet milling and then to high-pressure homogenization.
• the pH of the slurry be adjusted to a value of about 4.5 to about 6.5 before or during the performance of step b) to cause acidic or alkaline hydrolysis of the collagen during mechanical comminution largely avoided.
• the slurry may optionally be added with an oxidizing agent to achieve a bleaching and / or bactericidal effect.
• composition according to the invention which comprises insoluble fiber and / or insoluble proteins in addition to collagen particles, it is advantageous if they are added to the slurry prior to the performance of step b). These materials, together with the collagen material, are then subjected to comminution into particles of the appropriate order of magnitude.
• the particles according to the invention are obtained from collagen material as an aqueous dispersion which, depending on the weight ratio of the collagen material to the aqueous medium, has a viscous, creamy to pasty consistency and which can be used in this form for the production of foodstuffs.
• the particles obtained in step b) can be dried in an additional step c).
• the drying of the particles or the composition is preferably carried out by means of drum drying, spray drying, freeze drying or vacuum belt drying.
• hydrolysis of small amounts of collagen may occur, i.
• water-soluble products such as gelatine or collagen hydrolyzate are also formed.
• the products formed by hydrolysis as soluble materials can also contribute to a better redispersibility of the particles according to the invention after drying, as has been described in detail above.
• the proportion of the soluble materials formed in the mechanical comminution is generally insufficient for this purpose, it is preferred according to a further embodiment of the method according to the invention that after carrying out step b), and optionally before carrying out step c ), to the slurry is added a substantially water-soluble material.
• a composition can be obtained in which the particles of collagen material are dispersed in a matrix of the water-soluble material, whereby the subsequent redispersibility of the dried particles is markedly improved.
• the present invention further relates to the use of the above-described particles of collagen material or the above-described composition for producing foodstuffs.
• the particles or compositions according to the invention are suitable as fat substitutes in a wide variety of foods, in particular meat and sausage products, cheese imitations, instant powders for soups and sauces, dressings, mayonnaise, spreads, yoghurts and creams.
• the particles or compositions can also be used for the production of cosmetic or pharmaceutical products.
• the properties of the collagen particles can be exploited in particular in order to set the desired consistency of ointments or creams.
• dry, sterilized collagen particles can also be used as wound powder (or as a basis), with the high water binding capacity also being used.
• FIG. 1 shows a representation of a typical size distribution of the particles according to the invention.
• FIG. 2 an electron micrograph of the particles according to the invention.
• Example 1 Production of particles according to the invention from pig bones
• the starting material used was ossein from pig bones, i. defatted and demineralized bone material used. This was first coarsely crushed with a standard mincer, using a 5 mm perforated disc in a first pass and a 2 mm perforated disc in a subsequent second pass.
• an aqueous slurry was prepared from the coarsely crushed material, which was sufficiently flowable to be processed in a colloid mill. It was either a "Comitrol ® Processor Model 1500" (manufactured by Urschel Laboratories Inc.): used or a "PUC colloid mill type 60" with Umpumpvorrich- device (Probst & Class GmbH & Co. KG manufacturer).
• the mechanical comminution of the collagen material in the slurry was carried out initially at a gap width of the colloid mill of 3 mm and then again at a gap width of 1 mm.
• the slurry had a pasty, but still very grainy consistency after rubbing between fingers.
• the pH of the slurry was adjusted to about 5.5 by addition of caustic soda and about 0.5% by weight of hydrogen peroxide was added as a bactericide and bleach.
• the collagen material was then subjected to further mechanical comminution by means of a high-pressure homogenizer (Model Lab60 / 15 TBSI, manufacturer: APV / Gaulin).
• the high-pressure homogenization was in two successive passes with a working pressure 1000 bar, a submission and inlet temperature of 50 0 C and a throughput of 120 l / h performed. While after the first round when rubbing between the fingers still a very fine-grained structure was noticeable felt the resulting dispersion after the second round structureless and homogeneous.
• the determination of the average particle size and the polydispersity index as a measure of the size distribution of the collagen particles according to the invention was carried out by means of light scattering.
• a scattered light spectrometer S3500 manufactured: Particle Metrix
• two lasers with the wavelengths 780 and 405 nm and a nominal laser power of 3 mW was used.
• the dispersion of collagen particles obtained according to Example 1 was diluted with water to a dry mass fraction of about 5% by weight and added dropwise to the dispersion unit of the measuring instrument until a particle concentration sufficient for the measurement was reached. The measurement was carried out and evaluated automatically according to the instructions of the device manufacturer.
• FIG. 1 shows a representation of a typical size distribution of the particles according to the invention, which was determined by the measuring method described above.
• the height of the individual columns (y-axis) corresponds to the relative number of particles in the respective size range (x-axis, logarithmic scale).
• average particle diameters in the range from about 40 ⁇ m to about 80 ⁇ m with a polydispersity index of greater than 0.3 typically resulted.
• the mean particle diameter in the size distribution shown in FIG. 1 is 68.5 ⁇ m, with a polydispersity index of 0.47.
• Example 3 Preparation of a composition of collagen particles and wheat fibers
• Example 2 The preparation was carried out as described in Example 1, wherein immediately before carrying out the high-pressure homogenization, an amount of wheat fibers corresponding to the dry mass of collagen material was added to the slurry. At the same time, an appropriate amount of water was also added so that the total dry matter content in the slurry remained essentially unchanged.
• Example 2 The two passes of the high-pressure homogenization were then carried out as described in Example 1, whereby a structureless and homogeneous product was also obtained in the rubbing between the fingers.
• the calorie content of the product can be halved.
• a spray-drying machine of the type Niro P 6.3 with an externally mixing two-fluid nozzle (diameter 2 mm) was used.
• the dispersion of collagen particles obtained according to Example 1 was heated to about 64 to 68 0 C and pumped with a peristaltic pump to the two-fluid nozzle of the spray dryer.
• 10% by weight of collagen hydrolyzate (based on the collagen particles) were previously used as soluble matrix material in the dispersion. terial added to improve the redispersibility of the dried particles.
• Nozzle / atomizing
• the dispersion of collagen particles and wheat fibers obtained according to Example 3 was applied to a drum dryer (R. Simon (Dryers) Ltd., 300 mm diameter and 200 mm width) at a material feed of 12 kg / h, a temperature of 130 0 C and a residence time dried for about 25 s.
• a drum dryer R. Simon (Dryers) Ltd., 300 mm diameter and 200 mm width
• FIG. 2 shows an electron micrograph of the roll-dried composition.
• Individual collagen particles according to the invention are identified by the reference numeral 10.
• the dry particles were readily redispersible in the preparation of the formulations.
• a first mix of water, cornstarch, lactic acid and saline was prepared, as well as a second mix of the remaining ingredients. Subsequently, both mixtures were mixed in a heatable "Stephan Cutter UMC 5 electronic" at 600 rev / min and a temperature of 80 0 C for about 3 min.
• the cheese according to the invention contains significantly less fat and a higher proportion of water, which is bound by the collagen particles in comparison to the comparative preparation. Nevertheless, in the sensory evaluation both preparations have a comparable texture.
• a low-fat mayonnaise and a low-fat dressing with collagen particles according to the invention were prepared according to the composition given in Table 3 (all figures in percent by weight): Table 3
• a first mix of water, mustard, vinegar and citric acid was made, as well as a second mix of the remaining ingredients except the oil. Subsequently, both mixtures were mixed in a heated "Stephan cutter UMC 5 electronic" at 600 rpm for about 3 minutes (the mayonnaise at a temperature of 60 0 C and the dressing at 25 0 C). Thereafter, the oil was added and mixed for an additional minute under the same conditions.
• the example preparations contain more water and significantly less fat compared to normal mayonnaise (about 80% fat) and commercial dressings (30-50% fat).
• normal mayonnaise about 80% fat
• commercial dressings (30-50% fat).
• yoghurt 0.75% by weight of collagen particles were dispersed in cow's milk with a fat content of 0.5% and heated to 90 ° C. After cooling to 38 ° C., the yoghurt culture was added and the mixture was incubated at 38 ° C. until the target pH was reached.
• a control sample was prepared in the same way without the addition of collagen particles.
• the yogurt with the collagen particles according to the invention has, in contrast to the comparison sample, a smooth, creamy texture. In addition, it shows no syneresis, which is due to the water-binding properties of the collagen particles.
• a reduced fat chocolate nut spread was prepared with the composition shown in Table 4 (all percentages by weight):
• a first mixture of water, konjac and instant starch was prepared and a second mixture of collagen particles, sucrose, dextrose, fructose, nutriose and skimmed milk powder. Subsequently, both mixtures were mixed in a heatable "Stephan Cutter UMC 5 electronic" at 600 U / min and a temperature of 25 0 C for about 3 min. Thereafter, a mixture of nut paste, chocolate, cocoa and flavor was added and mixed for an additional minute under the same conditions.
• the spread contains more water and significantly less fat and carbohydrates.
• the carbohydrates were in this case z.T. replaced by the sugar substitute Nutriose.

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• Food Science & Technology (AREA)
• Polymers & Plastics (AREA)
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• Proteomics, Peptides & Aminoacids (AREA)
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• 2008
  • 2008-07-31 DE DE102008036576A patent/DE102008036576A1/de not_active Withdrawn
• 2009
  • 2009-07-22 EP EP09780940A patent/EP2303033A2/de not_active Withdrawn
  • 2009-07-22 CN CN2009801305273A patent/CN102112008B/zh not_active Expired - Fee Related
  • 2009-07-22 JP JP2011520434A patent/JP2011529463A/ja active Pending
  • 2009-07-22 WO PCT/EP2009/059442 patent/WO2010012640A2/de not_active Ceased
• 2011
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