CN112957375A - High-affinity shrimp shell calcium powder, preparation method thereof and application thereof in preparing medicines for treating calcium deficiency symptoms and/or diseases - Google Patents

High-affinity shrimp shell calcium powder, preparation method thereof and application thereof in preparing medicines for treating calcium deficiency symptoms and/or diseases Download PDF

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CN112957375A
CN112957375A CN202110374470.4A CN202110374470A CN112957375A CN 112957375 A CN112957375 A CN 112957375A CN 202110374470 A CN202110374470 A CN 202110374470A CN 112957375 A CN112957375 A CN 112957375A
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parts
calcium powder
shrimp shell
affinity
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CN112957375B (en
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涂宗财
李金林
晏侬洋
王美丹
马天新
刘俊
王辉
李小锋
张权
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Jiangxi Normal University
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K35/00Medicinal preparations containing materials or reaction products thereof with undetermined constitution
    • A61K35/56Materials from animals other than mammals
    • A61K35/612Crustaceans, e.g. crabs, lobsters, shrimps, krill or crayfish; Barnacles
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
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    • A61K9/141Intimate drug-carrier mixtures characterised by the carrier, e.g. ordered mixtures, adsorbates, solid solutions, eutectica, co-dried, co-solubilised, co-kneaded, co-milled, co-ground products, co-precipitates, co-evaporates, co-extrudates, co-melts; Drug nanoparticles with adsorbed surface modifiers
    • A61K9/146Intimate drug-carrier mixtures characterised by the carrier, e.g. ordered mixtures, adsorbates, solid solutions, eutectica, co-dried, co-solubilised, co-kneaded, co-milled, co-ground products, co-precipitates, co-evaporates, co-extrudates, co-melts; Drug nanoparticles with adsorbed surface modifiers with organic macromolecular compounds
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    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P19/00Drugs for skeletal disorders
    • A61P19/08Drugs for skeletal disorders for bone diseases, e.g. rachitism, Paget's disease
    • A61P19/10Drugs for skeletal disorders for bone diseases, e.g. rachitism, Paget's disease for osteoporosis
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    • AHUMAN NECESSITIES
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    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P3/00Drugs for disorders of the metabolism
    • A61P3/02Nutrients, e.g. vitamins, minerals
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P5/00Drugs for disorders of the endocrine system
    • A61P5/18Drugs for disorders of the endocrine system of the parathyroid hormones
    • A61P5/20Drugs for disorders of the endocrine system of the parathyroid hormones for decreasing, blocking or antagonising the activity of PTH

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Abstract

The invention relates to the field of medicines, in particular to high-affinity shrimp shell calcium powder, a preparation method thereof and application thereof in preparing medicines for treating calcium deficiency symptoms and/or diseases. The invention applies the high-affinity shrimp shell calcium powder with the loosening rate of not higher than 15 percent after being tabletted with the protein base material, not higher than 15 percent after being tabletted with the carbohydrate base material and not higher than 10 percent after being tabletted with the carbohydrate base material to the calcium deficiency symptoms and/or diseases, such as osteoporosis, rickets, osteomalacia, nutritional secondary hyperparathyroidism and postpartum convulsion, and has good curative effect.

Description

High-affinity shrimp shell calcium powder, preparation method thereof and application thereof in preparing medicines for treating calcium deficiency symptoms and/or diseases
Technical Field
The invention relates to the field of medicines, in particular to high-affinity shrimp shell calcium powder, a preparation method thereof and application thereof in preparing medicines for treating calcium deficiency symptoms and/or diseases.
Background
The canine calcium deficiency disease is a clinically common disease. Calcium deficiency can be divided into acute calcium deficiency and chronic calcium deficiency; the main manifestation of acute calcium deficiency is postpartum convulsion. The chronic common calcium deficiency diseases mainly comprise rickets, dog osteoporosis, nutritional secondary hyperparathyroidism and the like. With the increasing importance of the Chinese people on the symptoms of calcium deficiency, the demand for calcium is also increasing.
Crayfish (Procambrus clarkii) is a freshwater crayfish of Procambrus in America, belongs to crawfish family, and has annual output 70-80% of the whole freshwater crayfish. In China, the freshwater crayfishes are mainly distributed in the middle and lower reaches of Yangtze river such as Jiangsu, Hubei and Jiangxi and grow in water, the total output of the crayfishes in China exceeds 200 million tons, and the resources are very rich. In recent years, with the rapid development of the night market economy and the barbecue industry, the crayfish is used as one of the main roles of the night market economy and the barbecue industry, the market demand of the crayfish is increased extremely, and the rapid development of the crayfish processing industry is driven. However, the edible proportion of the crayfish is low, the adult crayfish is only 20-30%, the proportion of the crayfish head (including the crayfish shell and the crayfish gill) is as high as more than 70%, the crayfish head is usually directly discarded or simply processed into animal feed, the crayfish head is improperly utilized, the serious pollution problem or the resource waste is easily caused, and the crayfish head becomes a main obstacle for restricting the development of crayfish processing enterprises.
Research shows that the crayfish shell which is the by-product of crayfish processing is rich in nutrient components and active components such as calcium, chitin, protein and the like, wherein the calcium accounts for more than 30 percent by weight (calculated as calcium carbonate), and is a high-quality, safe and natural calcium resource. At present, shells of crayfish are mostly simply processed into animal feed, and a few shells of crayfish are used for extracting and preparing chitin, so that resource waste is serious. The development of the shrimp shell as a calcium resource has two difficulties, on one hand, the shrimp shell is hard in calcium, and is difficult to be applied to the food industry due to the taste problem after being processed into calcium powder; on the other hand, the shrimp shells are rich in calcium, chitin and other components, the compatibility of the shrimp shells with protein, starch, polysaccharide and the like is poor, and when the shrimp shells are prepared into dosage forms by taking the protein, the starch, the polysaccharide and the like as base materials, the addition amount of the shrimp shells is limited, and the application of the shrimp shells is influenced.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides high-affinity shrimp shell calcium powder, a preparation method thereof and application thereof in preparing medicines for treating calcium deficiency symptoms and/or diseases, wherein the high-affinity shrimp shell calcium powder has improved mouthfeel and good affinity with protein, starch, polysaccharide and the like.
In order to achieve the above objects, the present invention provides, in one aspect, a use of a high affinity shrimp shell calcium powder for the preparation of a medicament for the treatment of calcium deficiency symptoms and/or diseases;
wherein the loosening rate of the high-affinity shrimp shell calcium powder after being tabletted with a protein base material is not higher than 15%, the loosening rate after being tabletted with a carbohydrate base material is not higher than 15%, and the loosening rate after being tabletted with a carbohydrate base material is not higher than 10%;
wherein the calcium deficiency disease is selected from osteoporosis, rickets, osteomalacia, nutritional secondary hyperparathyroidism and postpartum convulsion.
The second aspect of the invention provides high-affinity shrimp shell calcium powder which contains shrimp shell calcium powder and a surface modifier,
wherein the surface modifier is composed of maltodextrin, pregelatinized starch, konjac powder, sodium carboxymethylcellulose and xanthan gum.
The third aspect of the invention provides a preparation method of high-affinity shrimp shell calcium powder, which comprises the following steps: preparing a surface modifier solution from a surface modifier, and then performing boiling granulation on the shrimp shell calcium powder to obtain the high-affinity shrimp shell calcium powder;
wherein the surface modifier is composed of maltodextrin, pregelatinized starch, konjac powder, sodium carboxymethylcellulose and xanthan gum.
The invention has the following advantages:
(1) according to the invention, maltodextrin, pregelatinized starch, konjac powder, sodium carboxymethylcellulose, xanthan gum and the like are used as surface modifiers, so that the taste of the shrimp shell calcium powder is effectively improved, and the affinity to protein, starch, polysaccharide and the like is improved. Preferably, the surface modifier is coated on the surface of the shrimp shell calcium powder particles by adopting a boiling granulation method to realize the surface modification of the shrimp shell powder, so that the mouthfeel of the shrimp shell calcium powder and the affinity to protein, starch, polysaccharide and the like are further improved.
(2) The calcium powder prepared by taking the natural shrimp shell as the raw material has natural calcium and high calcium content.
(3) The invention preferably adopts ultrasonic wave to assist organic acid to carry out acid treatment on the shrimp shells, removes harmful substances such as heavy metals and the like attached to the surfaces of the shrimp shells, and simultaneously furthest retains the calcium components in the shrimp shells.
(4) The invention preferentially adopts high-pressure boiling to soften the shrimp shells, thereby further improving the taste of the shrimp shell calcium powder.
(5) The invention preferably refines the shrimp shell calcium powder by high-pressure homogenization, and further improves the taste of the shrimp shell calcium powder.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the invention provides the application of high-affinity shrimp shell calcium powder in preparing a medicament for treating calcium deficiency symptoms and/or diseases;
wherein the loosening rate of the high-affinity shrimp shell calcium powder after being tabletted with a protein base material is not higher than 15%, the loosening rate after being tabletted with a carbohydrate base material is not higher than 15%, and the loosening rate after being tabletted with a carbohydrate base material is not higher than 10%;
wherein the calcium deficiency disease is selected from osteoporosis, rickets, osteomalacia, nutritional secondary hyperparathyroidism and postpartum convulsion.
According to the invention, the method for detecting the loosening rate comprises the following steps: taking 100 compressed tablets, putting into a glass bottle, wherein the volume of the tablets is about 1/3, sealing the bottle, shaking up and down 5 times with strong force of hands to obtain loose tablets after the tablets are scattered into small blocks, and calculating the loose tablet rate according to the following formula:
the loose piece rate is (number of loose pieces per 100 pieces in 100 pieces) × 100%.
In a second aspect, the invention provides high-affinity shrimp shell calcium powder, which contains shrimp shell calcium powder and a surface modifier;
wherein the surface modifier is composed of maltodextrin, pregelatinized starch, konjac powder, sodium carboxymethylcellulose and xanthan gum.
Wherein the pregelatinized starch is pregelatinized starch which accords with the national standard GB/T38573-2020 pregelatinized starch.
The inventor of the invention finds that the shrimp shell calcium powder with high affinity can be obtained by modifying the shrimp shell calcium powder with a surface modifier consisting of maltodextrin, pregelatinized starch, konjac powder, sodium carboxymethylcellulose and xanthan gum, namely, the shrimp shell calcium powder has higher affinity with protein, starch, polysaccharide and the like, and the taste of the shrimp shell calcium powder can be improved.
According to the present invention, the content of the surface modifier may be varied within a wide range, and in order to further improve the affinity of the high-affinity shrimp shell calcium powder for proteins, starch, polysaccharides, etc., and further improve the mouthfeel thereof, it is preferable that the content of the surface modifier is 4 to 10 parts by weight, for example, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, with respect to 100 parts by weight of the shrimp powder.
According to the present invention, the content of each component in the surface modifier may be changed within a wide range, and in order to further improve the affinity of the high-affinity shrimp shell calcium powder for proteins, starch, polysaccharides, etc. and further improve the texture, it is preferable that the content of the pregelatinized starch is 30 to 75 parts by weight (for example, 30 parts by weight, 31 parts by weight, 32 parts by weight, 33 parts by weight, 35 parts by weight, 37 parts by weight, 40 parts by weight, 43 parts by weight, 45 parts by weight, 47 parts by weight, 50 parts by weight, 53 parts by weight, 55 parts by weight, 57 parts by weight, 60 parts by weight, 63 parts by weight, 65 parts by weight, 67 parts by weight, 70 parts by weight, 73 parts by weight, 75 parts by weight) relative to 100 parts by weight of maltodextrin), and the content of the konjac flour is 8 to 25 parts by weight (for example, 8 parts by weight, 10 parts by weight, 75 parts by weight, or more, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 17 parts by weight, 20 parts by weight, 23 parts by weight, 25 parts by weight), a content of the sodium carboxymethylcellulose is 15 to 40 parts by weight (for example, may be 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, 27 parts by weight, 30 parts by weight, 33 parts by weight, 35 parts by weight, 37 parts by weight, 40 parts by weight), a content of the xanthan gum is 8 to 25 parts by weight (for example, may be 8 parts by weight, 10 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 17 parts by weight, 18 parts by weight, 20 parts by weight, 23 parts by weight, 25 parts by weight).
According to the invention, the content of each component in the surface modifier can be changed in a wide range, and in order to further improve the affinity of the high-affinity shrimp shell calcium powder for protein, starch, polysaccharide and the like and further improve the mouthfeel of the high-affinity shrimp shell calcium powder, the high-affinity shrimp shell calcium powder is preferably of a core-shell structure with the shrimp shell calcium powder as a core and the surface modifier as a shell.
Wherein the particle size of the core-shell structure can be preferably 80-120 meshes.
In a third aspect, the invention provides a preparation method of high-affinity shrimp shell calcium powder with a core-shell structure, which comprises the following steps: preparing a surface modifier solution from a surface modifier, and then performing boiling granulation on the shrimp shell calcium powder to obtain the high-affinity shrimp shell calcium powder;
wherein the surface modifier is composed of maltodextrin, pregelatinized starch, konjac powder, sodium carboxymethylcellulose and xanthan gum.
By the preparation method provided by the invention, the high-affinity shrimp shell calcium powder with a core-shell structure and a surface modifier as a shell can be obtained.
According to the present invention, the amount of the surface modifier may be varied within a wide range, and in order to further improve the affinity of the high-affinity shrimp shell calcium powder for proteins, starch, polysaccharides, etc., and further improve the taste thereof, it is preferable that the amount of the surface modifier is 4 to 10 parts by weight, for example, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, relative to 100 parts by weight of the shrimp powder.
According to the present invention, the content of each component in the surface modifier may be changed within a wide range, and in order to further improve the affinity of the high-affinity shrimp shell calcium powder for proteins, starch, polysaccharides, etc. and further improve the texture, it is preferable that the content of the pregelatinized starch is 30 to 75 parts by weight (for example, 30 parts by weight, 31 parts by weight, 32 parts by weight, 33 parts by weight, 35 parts by weight, 37 parts by weight, 40 parts by weight, 43 parts by weight, 45 parts by weight, 47 parts by weight, 50 parts by weight, 53 parts by weight, 55 parts by weight, 57 parts by weight, 60 parts by weight, 63 parts by weight, 65 parts by weight, 67 parts by weight, 70 parts by weight, 73 parts by weight, 75 parts by weight) relative to 100 parts by weight of maltodextrin), and the content of the konjac flour is 8 to 25 parts by weight (for example, 8 parts by weight, 10 parts by weight, 75 parts by weight, or more, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 17 parts by weight, 20 parts by weight, 23 parts by weight, 25 parts by weight), a content of the sodium carboxymethylcellulose is 15 to 40 parts by weight (for example, may be 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, 27 parts by weight, 30 parts by weight, 33 parts by weight, 35 parts by weight, 37 parts by weight, 40 parts by weight), a content of the xanthan gum is 8 to 25 parts by weight (for example, may be 8 parts by weight, 10 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 17 parts by weight, 18 parts by weight, 20 parts by weight, 23 parts by weight, 25 parts by weight).
According to the invention, the concentration of the surface modifier solution can vary within wide limits, preferably the concentration of the surface modifier solution is from 5 to 8% by weight, for example 5%, 6%, 7%, 8% by weight.
According to the invention, preferably, the boiling granulation can be carried out in a boiling granulator, and during the granulation, the boiling height of the material is preferably not higher than the height of an atomizing nozzle of the boiling granulator through the air intake quantity.
According to the present invention, preferably, in the boiling granulation process, the air inlet temperature of the boiling granulator is 100-; the air outlet temperature is 60-80 deg.C, such as 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, and 80 deg.C.
Preferably, the spray liquid flow rate can be adjusted according to the outlet air temperature.
According to the invention, the time for boiling granulation can be selected in a wide range, and preferably, the boiling granulation is stopped when the water content of the material reaches 2-3 wt%, so that the high-affinity shrimp shell calcium powder is obtained.
According to the invention, the particle size of the high-affinity shrimp shell calcium powder is not particularly limited, and can be the particle size of the particles obtained by conventional boiling granulation, and preferably, the particle size of the high-affinity shrimp shell calcium powder can pass through a 20-40 mesh sieve.
According to the invention, the shrimp shell calcium powder can be various conventional shrimp shell calcium powders, and the affinity and the mouthfeel of the shrimp shell calcium powder to protein, starch, polysaccharide and the like can be improved as long as the affinity modification is carried out according to the method provided by the invention. However, the inventors of the present invention have found in their studies that the above effects can be further improved by using a shrimp shell calcium powder obtained by sequentially subjecting shrimp shells to an acid treatment, primary drying, pulverization, softening, pulverization, and secondary drying, and that harmful substances such as heavy metals attached to the shrimp shells can be effectively removed while maximally retaining calcium components in the shrimp shells.
According to the present invention, the acid used in the acid treatment may be a conventionally used food grade acid, for example, acetic acid, citric acid, malic acid, etc., preferably acetic acid.
The concentration of the acid is not particularly limited, and preferably, the concentration of the acid, for example, acetic acid is 0.1 to 0.5% by weight, and for example, may be 0.1%, 0.2%, 0.3%, 0.4%, 0.5% by weight.
The amount of the acid can be selected within a wide range, and preferably, the ratio of the shrimp shell to the acid solution is 1:5-10 by weight, for example, 1:5, 1:6, 1:7, 1:8, 1:9, 1: 10.
According to a preferred embodiment of the present invention, the method of acid treatment comprises: performing acid treatment on shrimp shells in an acetic acid solution with the concentration of 0.1-0.5 wt%, wherein the feed-liquid ratio of the shrimp shells to the acetic acid solution is 1: 5-10.
According to the invention, in order to further improve the quality of the prepared high-affinity shrimp shell calcium powder, the acid treatment is preferably carried out under the ultrasonic condition.
Wherein the conditions of the ultrasound can be varied within a wide range, preferably the ultrasound has a power of 0.4 to 0.6 watts per square centimeter (e.g., can be 0.4 watts per square centimeter, 0.45 watts per square centimeter, 0.5 watts per square centimeter, 0.55 watts per square centimeter, 0.6 watts per square centimeter, wherein the area is the bottom area of the container), and the ultrasound has a time of 1 to 1.5 hours (e.g., can be 1 hour, 1.1 hour, 1.2 hours, 1.3 hours, 1.4 hours, 1.5 hours).
According to the present invention, the method of the first drying is not particularly limited, and it may be various drying methods conventionally used in the art, and preferably hot air drying.
Preferably, the conditions of the first drying include: the drying is carried out at 60-80 deg.C (for example, 60 deg.C, 63 deg.C, 65 deg.C, 68 deg.C, 70 deg.C, 73 deg.C, 75 deg.C, 78 deg.C, 80 deg.C) for 5-7 wt% (for example, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%) of water content.
According to the present invention, the method of pulverization is not particularly limited, and it may be carried out in a conventional pulverizer.
According to the invention, the softening is preferably carried out by a high-temperature and high-pressure cooking method, and specifically, the softening method comprises the following steps: mixing the pulverized material with water at a weight ratio of 1:3-5 (e.g. 1:3, 1:3.3, 1:3.5, 1:3.8, 1:4, 1:4.3, 1:4.5, 1:4.8, 1:5), and steaming at 0.1-0.15MPa (e.g. 0.1MPa, 0.11MPa, 0.12MPa, 0.13MPa, 0.14MPa, 0.15MPa) for 1-1.5h (e.g. 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5 h).
According to the present invention, the method of the refinement is also not particularly limited as long as the shrimp shell calcium powder can be refined to a desired particle size. According to a particularly preferred embodiment of the invention, the refining is carried out on a colloid mill, in particular the method of refining comprises colloid mill milling, 80-120 mesh filtration, a first homogenization and a second homogenization, which are carried out sequentially.
Wherein, the grinding times of the colloid mill can be 3 to 5 times.
Wherein, preferably, the pressure of the first homogenization is smaller than that of the second homogenization.
Preferably, the pressure of the first homogenization is 14 to 16MPa, and may be, for example, 14MPa, 14.5MPa, 15MPa, 15.5MPa, or 16 MPa.
Preferably, the pressure of the second homogenization is 30 to 40MPa, and may be, for example, 30MPa, 33MPa, 35MPa, 38MPa, or 40 MPa.
Wherein, during colloid milling, water can be added according to the situation, preferably, during colloid milling, the weight ratio of the shrimp shell calcium powder to water is 1:6-10 (for example, 1:6, 1:6.3, 1:6.5, 1:6.8, 1:7, 1:7.3, 1:7.5, 1:7.8, 1:8, 1:8.5, 1:9, 1:9.5 and 1: 10). It will be appreciated that if the proportion of water added during softening is sufficient, the colloid mill may not add additional water, and if it is not, the appropriate water may be added to make up the proportion.
According to the present invention, the method of the second drying is not particularly limited, and may be a conventional various drying method, and preferably, the second drying is spray drying.
The drying time is preferably such that the water content of the obtained shrimp shell calcium powder is 2-7 wt%.
Preferably, the air inlet temperature of the spray drying is 200-240 ℃, and the air outlet temperature is 80-100 ℃.
According to the invention, the method preferably further comprises sieving the second dried shrimp shell calcium powder through a 200-mesh sieve.
According to the present invention, the shrimp shell calcium powder may be derived from any shrimp, for example, a shrimp shell calcium powder which is required to be modified to improve its affinity for proteins, fats or saccharides, for example, a shrimp shell calcium powder derived from crayfish.
According to a particularly preferred embodiment of the invention, the preparation method of the shrimp shell calcium powder comprises the following steps:
1) acid treatment: selecting fresh shrimp shells, carrying out ultrasonic treatment in acetic acid solution with the concentration of 0.4-0.5 wt%, wherein the material-liquid ratio is 1:9-10 in terms of total amount, and the ultrasonic power is as follows: 0.55-0.6 watt/square centimeter, the area is the bottom area of the container), and the time is 1.4-1.5 hours.
2) Drying and crushing: drying the shrimp shell after acid treatment at 75-80 ℃ until the water content is 5-5.5 wt%, and then crushing by a crusher to obtain coarse shrimp shell calcium powder.
3) Softening: mixing the crude shrimp shell calcium powder and water according to the mass ratio of 1:4.3-5, and boiling by adopting a pressure cooker, wherein the pressure is controlled to be 0.13-0.15MPa, and the boiling time is 1-1.2 hours.
4) Thinning: adding 2.5-3.5 times of water into the softened material, pulverizing for 3-5 times by using a colloid mill, filtering with 105-mesh filter cloth and 120-mesh filter cloth, homogenizing the filtrate twice by using a homogenizer, wherein the first homogenizing pressure is controlled at 14-14.5MPa, and the second homogenizing pressure is controlled at 38-40 MPa.
5) Spray drying: drying the refined material by a spray drying tower at the air inlet temperature of 235-240 ℃ and the air outlet temperature of 95-100 ℃ until the water content is 4-7 wt%, and then sieving by a 200-mesh sieve to obtain the fine shrimp shell calcium powder.
6) Surface modification: the mixture of maltodextrin, pregelatinized starch, konjac powder, sodium carboxymethylcellulose and xanthan gum is used as a surface modifier, and boiling granulation is adopted to carry out boiling granulation on the fine shrimp shell calcium powder.
Wherein the surface modifier is used in an amount of 4 to 6 parts by weight relative to 100 parts by weight of the shrimp meal. The air inlet temperature of the boiling granulator is 100-150 ℃; the air outlet temperature is 60-80 ℃.
Wherein, relative to 100 weight parts of maltodextrin, the content of the pregelatinized starch is 30-35 weight parts, the content of the konjac powder is 14-16 weight parts, the content of the sodium carboxymethyl cellulose is 18-22 weight parts, and the content of the xanthan gum is 14-16 weight parts.
When the shrimp shell calcium powder obtained by the preferable preparation method of the shrimp shell calcium powder is subjected to subsequent affinity and taste modification under the preferable surface modifier, the affinity and the taste of the shrimp shell calcium powder can be remarkably improved, and the dosage of the surface modifier can be reduced, so that the production cost can be reduced, and the effective content of calcium in the obtained high-affinity calcium powder is improved.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, pregelatinized starch was purchased from Nanchang Green Biotechnology, Inc., cat # 20201128.
Examples 1 to 3
Preparation method for high-affinity calcium powder
The following operations were performed under the conditions shown in table 1.
1) Acid treatment: shells of fresh crayfish (i.e., procambarus clarkii) are selected and sonicated in an acetic acid solution.
2) Drying and crushing: drying the shrimp shells subjected to acid treatment by hot air, and then crushing by a crusher to obtain coarse shrimp shell calcium powder.
3) Softening: mixing the coarse shrimp shell calcium powder with water, and cooking by using a pressure cooker.
4) Thinning: adding water (the softened material is used as a material and the additionally added water is used as a liquid) into the softened material, crushing by using a colloid mill, filtering by using filter cloth, and homogenizing the filtrate twice by using a homogenizer.
5) Spray drying: drying the refined material by adopting a spray drying tower, and then sieving by a 200-mesh sieve to obtain the fine shrimp shell calcium powder.
6) Surface modification: the mixture of maltodextrin, pregelatinized starch, konjac powder, sodium carboxymethylcellulose and xanthan gum is used as a surface modifier, boiling granulation is adopted to carry out boiling granulation on the shrimp shell calcium powder, the air inlet amount is controlled, the boiling height of the material is required to be not higher than that of an atomizing nozzle, and the high-affinity shrimp shell calcium powder base material is obtained.
TABLE 1
Figure BDA0003010616680000111
Figure BDA0003010616680000121
Example 4
This example illustrates the preparation of high affinity calcium powder
The preparation of high affinity calcium powder was carried out according to the method of example 1, except that shrimp shell calcium powder: the ratio of the surface modifier is increased to 100: 15.
Example 5
This example illustrates the preparation of high affinity calcium powder
The preparation of high affinity calcium powder was carried out according to the method of example 3, except that the boiling granulation method was not used, but the fine shrimp shell calcium powder prepared in step 5) was directly mixed with the surface modifier uniformly and spray-dried.
Example 6
This example illustrates the preparation of high affinity calcium powder
The preparation of high affinity calcium powder was carried out according to the procedure of example 3, except that the acetic acid treatment was not carried out with acetic acid and the sonication was not carried out, but the acetic acid was replaced with an equimolar amount of citric acid and stirred for 3 hours.
Example 7
This example illustrates the preparation of high affinity calcium powder
The preparation of high affinity calcium powder was carried out according to the method of example 3 except that, instead of the softening step, in the step 3), after hot air drying, shrimp shells were mixed with water in a mass ratio of 1:8.5, followed by the refinement step of 4).
Example 8
This example illustrates the preparation of high affinity calcium powder
The preparation of high affinity calcium powder was carried out according to the method of example 1, except that only the first homogenization was carried out when the refinement was carried out.
Comparative example 1
This comparative example illustrates the preparation of a reference affinity calcium powder
The preparation of high affinity calcium powder was carried out as in example 3, except that xanthan gum was replaced with an equal amount of pectin.
Comparative example 2
This comparative example illustrates the preparation of a reference affinity calcium powder
The preparation of high affinity calcium powder was carried out as in example 3, except that the pregelatinization was replaced by an equal amount of starch.
Comparative example 3
This comparative example illustrates the preparation of a reference affinity calcium powder
Preparation of high affinity calcium powder was carried out in the same manner as in example 3 except that the refined powder of konjak was replaced with the same amount of glucose.
Comparative example 4
This comparative example illustrates the preparation of a reference affinity calcium powder
The preparation of high affinity calcium powder was carried out according to the method of example 3, except that maltodextrin was not added, but replaced with an equal amount of pregelatinized starch.
Comparative example 5
This comparative example illustrates the preparation of a reference affinity calcium powder
Preparation of high affinity calcium powder was carried out as in example 3, except that sodium carboxymethylcellulose was not added, but an equal amount of corn starch was substituted.
Test example 1
The test example is used to illustrate the removal ratio of heavy metals (cadmium is taken as an example)
The cadmium content of the sample was measured by inductively coupled plasma mass spectrometry (ICP-MS) according to the first method of GB 5009.268-2016 (national food safety Standard) for determination of multiple elements in food), and the removal ratio (%) of heavy metals in examples and comparative examples was calculated according to the following formula, and the higher the removal ratio, the more preferable the results were, as shown in Table 2.
The heavy metal removal ratio is (cadmium content in shrimp shell before cleaning-cadmium content in high affinity calcium powder)/cadmium content in shrimp shell before cleaning x 100%
TABLE 2
Examples Removal of heavy metals (cadmium for example)
Example 1 58%
Example 2 67%
Example 3 80%
Example 4 62%
Example 5 80%
Example 6 36%
Example 7 80%
Example 8 80%
Comparative example 1 80%
Comparative example 2 80%
Comparative example 3 80%
Comparative example 4 80%
Comparative example 5 80%
Comparing example 3 with examples 5 and 7-8 and comparative examples 1-5, it can be seen that the method of granulation, the method of softening, drying, refining, and the use of surface modifiers have substantially no effect on the removal rate of heavy metals.
Comparing examples 3 and 6, it can be seen that the acid treatment step has a greater effect on the removal rate of heavy metals, and that the clear proportion of heavy metals can be greatly increased under conditions where acetic acid is preferred and the sonication is carried out.
Comparing examples 1-3, it can be seen that under the conditions of example 3, in the case of significantly reduced surfactant usage (the increase in surfactant usage, due to the substantial absence of heavy metals, indirectly results in a decrease in the proportion of heavy metals in the finished product, as can be seen from the comparison of examples 1 and 4), the removal rate of heavy metals still reaches 80%, which is significantly improved compared to examples 1-2.
Test example 2
This test example is illustrative of taste assessment
A small spoon (about 0.5g) of the sample is scooped in the middle of the tongue, the sample is pushed by the tongue to move back and forth in the upper jaw after being held in the mouth for 5 seconds, whether the sample has granular sensation or not is sensed, and then the sample is transferred between the upper and lower groove teeth and lightly occluded to sense the hardness of the sample granules. The taste was divided into five grades according to experience (see table 3 for details), and the results were averaged from the taste evaluation results of 30 volunteers, with higher grades being more desirable. The evaluation results are shown in Table 4.
TABLE 3 table of taste grade of product
Figure BDA0003010616680000161
Table 4 taste scoring table for products
Examples Taste assessment
Example 1 4.1
Example 2 4.5
Example 3 4.8
Example 4 4.4
Example 5 4.5
Example 6 4.6
Example 7 3.2
Example 8 2.8
Comparative example 1 3.1
Comparative example 2 3.0
Comparative example 3 3.0
Comparative example 4 3.1
Comparative example 5 3.1
As can be seen from Table 4, the particle size and taste of the shrimp shell calcium powder are greatly reduced by the technical combination of the invention, and a foundation is laid for the application of the shrimp shell calcium powder in common foods, health-care foods and food nutrition enhancers.
Test example 3
This test example is for the purpose of illustrating affinity
The sample 90 parts, the food base material 10 parts, the protein food base material taking milk powder as an example, the carbohydrate food base material taking maltodextrin as an example, the carbohydrate base material taking sucrose powder as an example are uniformly mixed, a punching tablet machine is adopted for tabletting, the tabletting pressure is 20KN, the tablet thickness is 3mm, the loose piece rate (%) of the tablet is checked, the affinity of the material is judged according to the loose piece rate, the lower the loose piece rate is, the higher the affinity is, and the result is shown in Table 5.
Checking the loose piece rate: taking 100 compressed tablets, putting into a glass bottle, wherein the volume of the tablets is about 1/3, sealing the bottle, shaking up and down 5 times with strong force of hands to obtain loose tablets after the tablets are scattered into small blocks, and calculating the loose tablet rate according to the following formula:
the loose piece rate is (number of loose pieces per 100 pieces in 100 pieces) × 100%.
TABLE 4
Figure BDA0003010616680000171
As can be seen from Table 5, the shrimp shell calcium powder prepared by the treatment of the invention has good affinity with food base materials, can be well mixed with food base materials such as protein, carbohydrate, sugar and the like for application, and expands the application range.
Compared with the example 1 and the example 4, although the affinity of the product to the food matrix is increased, the effective content of calcium in the product is reduced due to the increase of the dosage of the surface modifier, and the range of the example 3 can effectively ensure high calcium content and the affinity of the product and the food matrix.
Comparing example 3 with example 6, it can be seen that the acid treatment step has a significant effect on the removal rate of heavy metals, but has little effect on the affinity of the final product to the food substrate.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (12)

1. The application of high-affinity shrimp shell calcium powder in preparing a medicament for treating calcium deficiency symptoms and/or diseases;
wherein the loosening rate of the high-affinity shrimp shell calcium powder after being tabletted with a protein base material is not higher than 15%, the loosening rate after being tabletted with a carbohydrate base material is not higher than 15%, and the loosening rate after being tabletted with a carbohydrate base material is not higher than 10%;
wherein the calcium deficiency disease is selected from osteoporosis, rickets, osteomalacia, nutritional secondary hyperparathyroidism and postpartum convulsion.
2. The high-affinity shrimp shell calcium powder is characterized by comprising shrimp shell calcium powder and a surface modifier;
wherein the surface modifier is composed of maltodextrin, pregelatinized starch, konjac powder, sodium carboxymethylcellulose and xanthan gum.
3. The high affinity shrimp shell calcium powder of claim 2, wherein the surface modifier is present in an amount of 4 to 10 parts by weight per 100 parts by weight of the shrimp powder;
preferably, the content of the pregelatinized starch is 30 to 75 parts by weight, the content of the konjac powder is 8 to 25 parts by weight, the content of the sodium carboxymethylcellulose is 15 to 40 parts by weight, and the content of the xanthan gum is 8 to 25 parts by weight, relative to 100 parts by weight of the maltodextrin.
4. The high-affinity shrimp shell calcium powder of claim 2 or 3, wherein the high-affinity shrimp shell calcium powder is of a core-shell structure with the shrimp shell calcium powder as a core and the surface modifier as a shell;
preferably, the particle size of the core-shell structure can pass through a 20-40 mesh sieve.
5. A preparation method of high-affinity shrimp shell calcium powder is characterized by comprising the following steps: preparing a surface modifier solution from a surface modifier, and then performing boiling granulation on the shrimp shell calcium powder to obtain the high-affinity shrimp shell calcium powder;
wherein the surface modifier is composed of maltodextrin, pregelatinized starch, konjac powder, sodium carboxymethylcellulose and xanthan gum.
6. The method as claimed in claim 5, wherein the surface modifier is used in an amount of 4-15 parts by weight on a dry weight basis relative to 100 parts by weight of the shrimp shell calcium powder;
preferably, the content of the pregelatinized starch is 30-75 parts by weight, the content of the konjac powder is 8-25 parts by weight, the content of the sodium carboxymethylcellulose is 15-40 parts by weight, and the content of the xanthan gum is 8-25 parts by weight relative to 100 parts by weight of the maltodextrin;
preferably, the concentration of the surface modifier solution is 5 to 8 weight percent;
preferably, in the boiling granulation process, the air inlet temperature is 100-150 ℃, and the air outlet temperature is 60-80 ℃; and/or
The water content of the high-affinity shrimp shell calcium powder is 2-3 wt%; and/or
The high-affinity shrimp shell calcium powder can pass through a sieve with the granularity of 20-40 meshes.
7. The method as claimed in claim 5 or 6, wherein the shrimp shell calcium powder is prepared by the method comprising: sequentially carrying out acid treatment, primary drying, crushing, softening, fine pulverization and secondary drying on the shrimp shells.
8. The method of claim 7, wherein the acid treatment process comprises: performing acid treatment on shrimp shells in an acetic acid solution with the concentration of 0.1-0.5 wt%, wherein the feed-liquid ratio of the shrimp shells to the acetic acid solution is 1: 5-10;
preferably, the acid treatment is performed under ultrasonic conditions;
preferably, the power of the ultrasonic wave is 0.4-0.6 watt/square centimeter, and the time of the ultrasonic wave is 1-1.5 hours.
9. The method of claim 7 or 8, wherein the conditions of the first drying comprise: drying at 60-80 deg.C for a time sufficient to obtain a material having a moisture content of 5-7 wt%; and/or
The second drying is spray drying, and the drying time is that the moisture content of the shrimp shell calcium powder is 2-7 wt%; preferably, the air inlet temperature of the spray drying is 200-240 ℃, and the air outlet temperature is 80-100 ℃.
10. The method of any of claims 7-9, wherein the softening process comprises: mixing the pulverized material with water at a weight ratio of 1:3-5, and steaming under 0.1-0.15MPa for 1-1.5 h.
11. The method according to any one of claims 7 to 10, wherein the refining method comprises colloid mill milling, 80-120 mesh filtration, first homogenization and second homogenization, which are performed sequentially;
preferably, the pressure of the first homogenizing is 14-16 MPa; and/or
The pressure of the second homogenizing is 30-40 MPa.
12. The method of any one of claims 5-11, wherein the shrimp shell calcium powder is shrimp shell calcium powder from crayfish.
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