WO2004063095A2 - Method for production of solvent for high solution of calcium, calcium powder with high solubility thereof and calcium liquid thereof - Google Patents
Method for production of solvent for high solution of calcium, calcium powder with high solubility thereof and calcium liquid thereof Download PDFInfo
- Publication number
- WO2004063095A2 WO2004063095A2 PCT/KR2004/000031 KR2004000031W WO2004063095A2 WO 2004063095 A2 WO2004063095 A2 WO 2004063095A2 KR 2004000031 W KR2004000031 W KR 2004000031W WO 2004063095 A2 WO2004063095 A2 WO 2004063095A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- calcium
- vinegar
- powder
- solution
- total acidity
- Prior art date
Links
- 239000011575 calcium Substances 0.000 title claims abstract description 750
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 721
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 718
- 239000000843 powder Substances 0.000 title claims abstract description 151
- 239000007788 liquid Substances 0.000 title claims abstract description 124
- 239000002904 solvent Substances 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title description 6
- 235000021419 vinegar Nutrition 0.000 claims abstract description 137
- 239000000052 vinegar Substances 0.000 claims abstract description 137
- 238000004090 dissolution Methods 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 40
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 146
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 99
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 73
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 46
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 39
- 239000008121 dextrose Substances 0.000 claims description 36
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 26
- 239000004310 lactic acid Substances 0.000 claims description 24
- 235000014655 lactic acid Nutrition 0.000 claims description 24
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 13
- 239000000284 extract Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000001694 spray drying Methods 0.000 claims description 4
- 235000009754 Vitis X bourquina Nutrition 0.000 claims description 3
- 235000012333 Vitis X labruscana Nutrition 0.000 claims description 3
- 240000006365 Vitis vinifera Species 0.000 claims description 3
- 235000014787 Vitis vinifera Nutrition 0.000 claims description 3
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- 238000001035 drying Methods 0.000 claims 1
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 229960005069 calcium Drugs 0.000 description 702
- 235000001465 calcium Nutrition 0.000 description 702
- 239000000243 solution Substances 0.000 description 172
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- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 14
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- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 6
- 238000013461 design Methods 0.000 description 6
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- 235000002906 tartaric acid Nutrition 0.000 description 6
- 210000002700 urine Anatomy 0.000 description 6
- ZAHDXEIQWWLQQL-IHRRRGAJSA-N Deoxypyridinoline Chemical compound OC(=O)[C@@H](N)CCCC[N+]1=CC(O)=C(C[C@H](N)C([O-])=O)C(CC[C@H](N)C(O)=O)=C1 ZAHDXEIQWWLQQL-IHRRRGAJSA-N 0.000 description 5
- 239000005909 Kieselgur Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 235000019658 bitter taste Nutrition 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 102000004067 Osteocalcin Human genes 0.000 description 4
- 108090000573 Osteocalcin Proteins 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
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- 208000029725 Metabolic bone disease Diseases 0.000 description 3
- 206010049088 Osteopenia Diseases 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 3
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- 235000011007 phosphoric acid Nutrition 0.000 description 3
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- 239000013589 supplement Substances 0.000 description 3
- 235000021076 total caloric intake Nutrition 0.000 description 3
- 206010006956 Calcium deficiency Diseases 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 244000132059 Carica parviflora Species 0.000 description 2
- 235000014653 Carica parviflora Nutrition 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- 102000002322 Egg Proteins Human genes 0.000 description 2
- 108010000912 Egg Proteins Proteins 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 210000000577 adipose tissue Anatomy 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 235000021120 animal protein Nutrition 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
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- 230000023555 blood coagulation Effects 0.000 description 2
- 230000037396 body weight Effects 0.000 description 2
- 210000000459 calcaneus Anatomy 0.000 description 2
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 description 2
- 239000001527 calcium lactate Substances 0.000 description 2
- 229960002401 calcium lactate Drugs 0.000 description 2
- 235000011086 calcium lactate Nutrition 0.000 description 2
- 235000019577 caloric intake Nutrition 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
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- 235000018823 dietary intake Nutrition 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
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- 235000019640 taste Nutrition 0.000 description 2
- VEPOHXYIFQMVHW-PVJVQHJQSA-N (2r,3r)-2,3-dihydroxybutanedioic acid;(2s,3s)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O.O1CCN(C)[C@@H](C)[C@@H]1C1=CC=CC=C1 VEPOHXYIFQMVHW-PVJVQHJQSA-N 0.000 description 1
- 241000427159 Achyranthes Species 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 244000037364 Cinnamomum aromaticum Species 0.000 description 1
- 235000014489 Cinnamomum aromaticum Nutrition 0.000 description 1
- 241000212948 Cnidium Species 0.000 description 1
- 102000015781 Dietary Proteins Human genes 0.000 description 1
- 108010010256 Dietary Proteins Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
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- 241000208688 Eucommia Species 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 244000241872 Lycium chinense Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 244000151018 Maranta arundinacea Species 0.000 description 1
- 235000010804 Maranta arundinacea Nutrition 0.000 description 1
- 241000083652 Osca Species 0.000 description 1
- 244000131316 Panax pseudoginseng Species 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
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- 150000001669 calcium Chemical class 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
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- 230000001615 calciuric effect Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
- CVSVTCORWBXHQV-UHFFFAOYSA-N creatine Chemical compound NC(=[NH2+])N(C)CC([O-])=O CVSVTCORWBXHQV-UHFFFAOYSA-N 0.000 description 1
- 230000000378 dietary effect Effects 0.000 description 1
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- 238000003384 imaging method Methods 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
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Classifications
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, 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
- A23L33/00—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
- A23L33/16—Inorganic salts, minerals or trace elements
-
- 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
Definitions
- the present invention relates to methods of preparing a solvent for dissolution of calcium, a calcium powder prepared using the solvent, and a calcium liquid prepared using the calcium powder. More particularly, the present invention relates to a method of preparing a solvent capable of enhancing the solubility of calcium, a method of preparing a calcium powder with remarkably enhanced solubility, based on the , dissolution of calcium in the solvent, and a method of preparing a calcium liquid, based on the dissolution of the calcium powder in vinegar.
- calcium is a constituent of bone and teeth, and is an inorganic substance involved in various biological reactions, such as enzyme activation, regulation of nervous excitation, muscle contraction and blood clotting.
- calcium which is an essential element for the body, plays critical roles in various biochemical functions of the body, for example, formation of bone and teeth, blood clotting, muscle contractions and relaxation, transmission of nervous signals, regulation of nervous excitation, regulation of permeability of plasma membrane, absorption of vitamin B ⁇ 2 , fusion of plasma membrane and cell division.
- Osteoporosis has become a severe disease in society. Osteoporosis is caused by decalcification. When calcium loss occurs, bone becomes weak, resulting in the production of the structure like a hornet' s nest. Such decalcified bone is thus weak. Therefore, it is easily fractured, even by daily physical actions, such as lifting of some materials and bending the body. Osteoporosis is generally recognized to commonly occur with advancing age, but can occur even in people with well-regulated hormone balance. Thus, it is very important to prevent the disease.
- the most effective method to form and maintain strong and healthy bone is to regularly ingest a suitable amount of calcium from early life to advanced life.
- the moderns ingest a large amount of animal proteins with improved economic welfare.
- the increased intake of animal proteins is known to stimulate calcium excretion
- the recommended daily amount of calcium is 700 mg for adults (ages 20 and older) and 800-900 mg for juveniles.
- juveniles in Korea were found to ingest about 500-600 mg of calcium, and not to meet the daily requirement of calcium (the nutrition evaluation part of the report for national health and nutrition survey, the Korean Health & Welfare Ministry, 1999) .
- the present invention aims to provide a method of preparing a solvent capable of producing highly soluble calcium powder, a method of preparing a calcium powder using the solvent, and a method of preparing a calcium liquid using the calcium powder.
- the present invention provides a method of preparing a solvent for dissolution of calcium, including mixing 97.14% (w/w) of apple vinegar with a total acidity of 6.6, 0.2% (w/w) of phosphoric acid, 0.15%
- the present invention provides a method of preparing a highly-soluble reprocessed calcium powder, including adding 17.50-20.00% (w/v) of calcium carbonate and 6.7-7.8% (w/v) of dextrose to the solvent prepared according to the above method, dissolving the calcium carbonate and the dextrose in the solvent, homogenizing the resulting solution and spray-drying the homogenized solution.
- the present invention provides a method of preparing a highly-soluble reprocessed calcium liquid, including dissolving the calcium powder prepared according to the immediately above method in a vinegar as a solvent.
- Fig. 1 is a graph showing the ' solubility of aqua calcium in various vinegar solutions
- Fig. 2 is a graph showing the solubility of aqua calcium in an apple vinegar solution A under various initial acidities
- Fig. 3 is a graph showing the solubility of nano calcium in an apple vinegar solution A under various initial acidities
- Fig. 4 is a graph showing the solubility of calcium carbonate in an apple vinegar solution A under various initial acidities
- Fig. 5 is a graph showing the solubility of aqua calcium and calcium carbonate in an apple vinegar solution A
- Fig. 6 is a graph showing the solubility of 2% aqua calcium in various organic acids under various initial acidities
- Fig. 7 is a graph showing the solubility of 3% aqua calcium according to various concentrations of acetic acid and lactic acid;
- Fig. 8 is a graph showing the solubility of 3% calcium carbonate according to various concentrations of acetic acid and lactic acid
- Fig. 9 is a graph showing the solubility of various calcium types according to concentrations of vinegar
- Fig. 10 is a contour map showing changes in pH of a calcium powder according to contents of calcium and dextrose
- Fig. 11 is a contour map showing changes in total acidity of a calcium powder according to contents of calcium and dextrose;
- Fig. 12 is a contour map showing changes in hydration rate of a calcium powder according to contents of calcium and dextrose
- Fig. 13 is a contour map showing changes in solubility of a calcium powder according to contents of calcium and dextrose
- Fig. 14 is a contour map showing changes in reduced sugar content of a calcium powder according to contents of calcium and dextrose;
- Fig. 15 is a contour map showing changes in total sugar content of a calcium powder according to contents of calcium and dextrose
- Fig. 16 is a contour map showing changes in solubilized calcium content of a calcium powder according to contents of calcium and dextrose
- Fig. 17 is a contour map showing changes in solubilized calcium content of a calcium solution that is prepared by dissolving a calcium powder in an acetic acid solution according to contents of calcium and dextrose;
- Fig. 18 is a graph showing overlapping of the above contour maps for the dependent variables for the preparation of a calcium powder.
- Calcium is water-insoluble and difficult to add to foods due to its bitterness. Also, because of its poor absorption properties into the body, calcium is mostly excreted. Therefore, in developing calcium products, calcium is urgently required to be improved in solubility and body absorbability.
- calcium-containing foods or pharmaceutical preparations should be first broken down and solubilized in the stomach while ionizing calcium ions.
- the absorption of calcium is affected by the breakdown rate and solubility of digested calcium diets or supplements. That is, the absorption of calcium increases as calcium diets or supplements are rapidly broken down and solubilized and as calcium ionization occurs at higher levels.
- a highly-soluble calcium powder was first prepared, and a calcium liquid was then prepared using the calcium powder, based on the results of Experimental Examples 1 to 4 of the present invention, as follows.
- Optimal solubility of calcium in vinegar was investigated by measuring solubility of three calcium types in four vinegar solutions, which are commercially available. Aqua calcium was found to be completely solubilized in all vinegar solutions in an amount of 2.0% (w/v) .
- aqua calcium used in an amount of 2.0% (w/v) concentration showed a similar solubility to that described immediately above, and nano calcium with low purity showed a low solubility.
- calcium carbonate displayed a similar solubility to the aqua calcium.
- a solvent is prepared by mixing 97.14%% (w/w) of apple vinegar with a total acidity of 6.6, 0.2% (w/w) of phosphoric acid, 0.15% (w/w) of lactic acid, 0.01% (w/w) of citric acid, 1.2% (w/w) of a tangle extract and 1.3% (w/w) of a malt extract.
- a highly soluble calcium powder is prepared by adding to the solvent 17.50-20.00% (w/v) of calcium carbonate and 6.7-7.8% (w/v) of dextrose, based on the total weight of the solvent, dissolving the calcium carbonate and the dextrose in the solvent, homogenizing resulting solution and spray-drying the homogenized solution.
- Vinegar is used as a major ingredient in the solvent for dissolution of calcium, and phosphoric acid and lactic acid are additionally added to the solvent to supplement the action of the vinegar.
- the organic acids were selected based on the data from the test for their effect on solubility on calcium. Acetic acid showed the highest positive effect on calcium solubility. However, rather than a single organic acid, a mixture of several organic acids was found to be more effective in solubilizing calcium. Thus, phosphoric acid and lactic acid are used as ingredients of the solvent for the solubilization of calcium.
- phosphoric acid and lactic acid which have a low volatility and a high gravity, are added to the solvent.
- an extract of filtrated glycosylated malts (15° Brix) for the removal of the bitterness and a heat-water extract of dried tangles for enrichment of trace elements such as iron, phosphor and magnesium are added to the solvent for dissolution of calcium.
- the dextrose serves as an excipient for spray-drying of the solvent in which calcium carbonate has been dissolved.
- the contents of the calcium carbonate and the dextrose are optimal amounts, which are determined by pH, total acidity, hydration rates and solubility of the calcium powder under various conditions, and Ca contents, reduced sugar contents and total sugar contents in the powder and a calcium solution prepared using the calcium powder.
- calcium carbonate and aqua calcium are preferable because of showing a distinct increase in solubility.
- calcium carbonate is used for the preparation of the calcium powder that is used in the preparation of the calcium liquid.
- the solvent is stirred to dissolve the added substances while not generating bubbles, and homogenized according to a method commonly used in the art.
- the resulting solution is spray-dried according to a method commonly used in the art to produce a calcium powder.
- the present method of preparing a calcium powder is more advantageous than conventional methods for the solubilization of calcium because bubbles caused by C0 2 production are generated in a relatively small amount.
- the present invention provides a method of preparing a calcium liquid, including dissolving in a vinegar solvent the calcium powder prepared by dissolving calcium carbonate and dextrose in the present solvent.
- the vinegar solution used for dissolution of calcium preferably has an initial acidity of 6.5.
- the vinegar solution preferably has a pH of 2, which is the most effective pH value on dissolution of calcium. That is, dissolution of KJ calcium powder is believed to be not greatly affected by the initial pH of a solvent, compared to other calcium forms, but the pH of the solvent is preferably 2 to allow for the calcium liquid to contain calcium of 2500 mg/100 ml or higher.
- the solvent for preparation of a calcium liquid is a mixture of 91.6298 wt% of breed vinegar with a total acidity of over 6.5, 1.4000 wt% of glucose, 0.3500 wt% of phosphoric acid, 0.3000 wt of lactic acid, 0.1000 wt% of acetic acid, 0.0200 wt% of citric acid, 0.0001 wt% of an antifoamer and 0.0001 wt% of grape flavor.
- the calcium powder is preferably dissolved in the vinegar solution in an amount of 10% (w/v) .
- the calcium liquid is supplemented with activated carbon to improve the unfavorable sensory qualities including the bitterness and burning taste, which are caused by the added calcium.
- the activated carbon is preferably added in an amount of 0.03% (w/v).
- the calcium powder is preferably added to the vinegar solution in an amount of 10% (w/v) based on the total weight of the vinegar solution.
- the used amount of the calcium powder was determined taking into overall consideration concentration of calcium dissolved in the solvent, changes in total acidity and pH of the solvent, and the solvent' s brown color intensity, turbidity and color intensity, and the like.
- the calcium liquid is preferably filtered to remove impurities according to a method commonly used in the art, and preferably, by a filtration method using diatomaceous earth. After being filtered, the calcium liquid is preferably sterilized using a sterilizer at a high temperature for a very short time.
- the absorption rate of calcium contained in the calcium liquid was determined by measuring bone mineral density, serum calcium levels and serum osteocalcin levels in human subjects who have consumed a calcium-enriched herbal pouch drink containing the calcium liquid.
- the solvent capable of improving the solubility of calcium, the highly soluble calcium powder prepared using the solvent and the calcium liquid prepared using the calcium powder according to the present invention can be used as a food additive or a beverage, and is thus an useful invention in the food industry.
- apple vinegar A (Samhan-Saehan Company, total acidity: 6.6) and B (Daehakcheon Company, total acidity: 6.0) and persimmon vinegar C (Samhan-Saehan Company, total acidity: 4.1) and D (Daehakcheon Company, total acidity: 5.8), which are commercially available.
- 50 ml of each vinegar solution was put into a 100-ml Erlenmeyer flask.
- Aqua calcium (34.08% calcium, Bio-DeltaKorea Company) was added to the vinegar solution in various amounts of 0.5%, 1.0%, 1.5% and 2.0% (w/v). After the solution was agitated at 200 rpm at 30°C overnight, the solubility of calcium was analyzed.
- the vinegar solution D was found to have the highest initial pH of 3.29, and the next highest initial pH value was found in the vinegar solution B, C and then A.
- the vinegar solution C showed the highest change in pH, and the pH values of each vinegar solution increased with increasing amounts of calcium added.
- the vinegar solution A displayed the highest initial total acidity of 6.68, while the vinegar solution C showed the lowest initial total acidity.
- the vinegar solution C displayed the highest total acidity, while other vinegar solutions showed similar total acidity to their initial total acidity.
- the persimmon vinegar solutions C and D showed a higher turbidity and brown color intensity than the apple vinegar solutions A and B.
- the apple vinegar solutions showed a lower residual calcium amount than the persimmon vinegar solutions.
- the vinegar solution A is relatively low priced in comparison with other vinegar solutions, and found to have a higher initial total acidity than other vinegar solutions. Also, since the vinegar solution A showed high total acidity even after being supplemented with aqua calcium, it is believed to be able to dissolve a larger amount of calcium. Thus, the ' vinegar solution A was determined to be suitable in Experimental Example 2, below.
- the initial pH value of the vinegar solution decreased with increasing initial total acidity.
- the pH value increased as calcium was added, like the report described by Shin HS and Kim GH (Effect of preparation conditions of eggshell calcium and organic acids on ionization of calcium, the Journal of Korean Agrichemistry. 40, 531-535, 1997), in which, when eggshell calcium was added to a highly acidic solution in an amount of 1%, the pH of the solution was increased to a highly alkali pH value, and such a strong alkali increased ionization of calcium.
- the vinegar solution with an initial total acidity of 2 was added with 3% of aqua calcium, it showed a much lower total acidity than other samples. Turbidity and brown color intensity of the vinegar solutions were found to slightly increase with increasing concentrations of calcium added.
- the residual calcium amount increased with increasing concentrations of calcium. The highest residual calcium amount was observed when the vinegar solution with an initial total acidity of 2 was added with 3% or aqua calcium, and this case was found to have reduced calcium solubility.
- vinegar solutions added with nano calcium pH and total activity values were found to be similar to those shown in the cases of using aqua calcium, turbidity and brown color intensity increased with increasing concentrations of calcium added. Also, residual calcium amount was found to increase with increasing concentrations of calcium added, leading to a reduction in the solubility of calcium.
- the vinegar solution with an initial total acidity of 2 displayed a much lower total acidity than the case of being added with 0.5% and 1% of calcium, and showed a much lower calcium solubility than the case of being ' added with 0.5% and 1% of calcium.
- the vinegar solution A showed higher pH values when added with calcium carbonate than when added with coral carbonate. However, in the calcium concentrations of 6% or higher, the vinegar solution A displayed higher pH values when added with coral carbonate. The pH value was found to increase with increasing concentrations of calcium added. Higher total acidities were observed in the vinegar solution A that had been added with 4% and 5% aqua calcium and with 6% or higher calcium carbonate. Both of the calcium forms displayed similar residual calcium amounts to each other. Solubility of calcium decreased inversely with concentrations of calcium added.
- solubility of calcium in the acetic acid and lactic acid solutions was increased in the initial total acidity of up to 4, but slightly increased in the initial total acidity of 6 in comparison with the same solutions with an initial total acidity of 4.
- Calcium was not dissolved in all of the tartaric acid solutions.
- citric acid solutions calcium started to dissolve in the initial total acidity of 4, and its solubility was greatly increased in the initial total acidity of 6.
- the acetic acid solution dissolved 594.35 mg% of aqua calcium, and thus, showed the highest calcium solubility.
- the above result in that the vinegar solution with an initial total acidity of 2 dissolved 722.25 mg% of aqua calcium indicates that the organic acids can dissolve higher amounts of calcium when used in combination than when used individually.
- the apple vinegar solution A displayed higher pH values when added with aqua calcium than when added with nano calcium or calcium carbonate.
- the pH values decreased with increasing concentrations of vinegar.
- the total acidity was greatly increased in the vinegar solutions with a vinegar concentration of 40% or higher.
- the calcium carbonate (calcium content: 48.9% capable of being used as a food additive) used in Experimental Example 2, was used in this test.
- a solvent used in this test was prepared by mixing the apple vinegar solution A used in Experimental Example 1, phosphoric acid, lactic acid, citric acid, a tangle extract and a malt extract in a ratio of 97.14%,
- the tangle extract was prepared by an extraction method commonly used in the art, and the malt extract (15° Brix) was prepared by glycosylation at 60°C for 6 hrs.
- a solvent for calcium was prepared by mixing without generation of bubbles a brewed vinegar, phosphoric acid, lactic acid, citric acid, a tangle extract and a malt extract.
- Dependent variables affected by the factor variables that is, quality factors of the calcium powder, including water content (Yi) , pH (Y 2 ) , color intensity (Y 4 ) , brown color intensity (Y 5 ) , hydration rate (Yg) , dissolution rate (Y) , reduced sugar content (Yg) , total sugar content (Yg) , Ca content (Y ⁇ o) of the calcium powder and Ca content (Yn) of a calcium solution prepared using the calcium powder, were measured in independent three experiments, and their mean values were used in a regression analysis.
- a prediction by the regression analysis was performed with a SAS (statistical analysis system) program.
- SAS statistical analysis system
- a critical point was not a maximum point or a minimum point but a saddle point as a result of the regression analysis
- an optimal point was estimated by a ridge analysis, and the optimal condition for preparation of the calcium powder was analyzed by contour map and 3-D response surface analysis.
- a calcium powder was prepared by dispersing calcium carbonate and dextrose in various amounts as listed in Table 11 in the solvent and then stirring the solution for dissolution of the calcium carbonate and dextrose at 20°C for 12 hrs.
- a homogenizer was used to homogenize the particles. The homogenized solution was spray-dried in a spray-drier under predetermined conditions, thus yielding a calcium powder.
- the quality of the calcium powder was analyzed in a powder form (hereinafter referred to simply as "calcium powder”) and in a liquid form (hereinafter referred to simply as “calcium solution”) .
- a calcium solution in the liquid form was prepared by adding the calcium powder to an acetic acid solution in an amount of 5% (w/v) , agitating the mixture at 200 rpm for 30°C overnight to allow for the calcium powder to be dissolved in the acetic acid solution, and filtering the resulting mixture twice.
- the water content of the calcium powder and the calcium solution was measured three times, based on the Korean food standard code.
- the Hunter's color and brown color intensity of each calcium solution was analyzed using an UV- spectrophotometer.
- the hydration rate was measured by dissolving 1% (w/v) of the calcium powder in distilled water, filtering the solution with a filter, measuring the weight of the calcium remained on the filter, and expressing the content of calcium dissolved in the distilled water as %.
- % hydration was calculated according to the following equation: (the weight of calcium powder before dissolution - the weight of calcium remained on a filter after dissolution) /the weight of calcium powder before dissolution x 100.
- the dissolution rate was measured by passing each calcium solution through a pre-weighed filter, measuring the weight of calcium remained on the filter, and expressing the content of calcium dissolved in the acetic acid solution as %. That is, % hydration was calculated according to the following equation: (the weight of calcium powder before dissolution - the weight of calcium remained on a filter after dissolution) /the weight of calcium powder before dissolution x 100.
- the reduced sugar - content was measured by a DNS method after diluting the calcium solution. Total sugar content was measured according to the same method as in the measurement of the reduced sugar content after adding 20 ml of the calcium solution to 6N HCl to decompose calcium.
- the Ca content of the calcium powder was measured by incinerating a predetermined amount of the calcium powder, decomposing the calcium powder in 6N HCl and subjecting suitably diluted samples to analysis of Ca content using AAS (atomic absorption spectrometry) .
- AAS atomic absorption spectrometry
- the Ca content of the calcium solution was measured by AAS after the calcium solution was suitably diluted.
- the optimal condition for preparation of the calcium powder was predicted within an overlapped region when contour maps for the quality factors were overlapped.
- the calcium powder products prepared according to the 10 cases determined by the central composite design, were evaluated for water content, pH values and total acidity, and the results are given in Table 12, below. Also, the calcium powder products were evaluated for hydration rates, dissolution rates and color intensities. The results are given in Table 13, below. Further, the calcium powder products were evaluated for Hunter 7 s color and brown color intensity, and the results are given in Table 14, below.
- the Ca contents of the calcium powder and the calcium solution, prepared by the central composite design, are given in the above Table 15.
- Response surface regression equations and contour maps, which were obtained using the data in Table 15, are given in the above Table 16 and Figs. 16 and 17.
- R 2 values of the regression equations for the Ca contents of the calcium powder and the calcium solution were 0.9973 and 0.9843 at the significance level of below 1%.
- the optimal condition for the calcium powder preparation according to the Ca Content is given in the above Table 17. Since the predicted stationary point was a saddle point, a ridge analysis was performed. As a result, the Ca contents of the calcium powder and the calcium solution were 372.38 mg/g and 2.96%, respectively.
- the calcium powder preparation condition was the calcium content of 19.22% and the dextrose content of
- the calcium powder preparation condition to achieve the maximum Ca content in a calcium solution was the calcium content of 19.39% and the dextrose content of 1.02%.
- the optimal range for the calcium powder preparation condition was predicted by overlapping the contour maps for the pH, total acidity, hydration rate and dissolution rate of the calcium powder products according to the preparation conditions, the Ca contents of the calcium powder and the calcium solution, and the reduced sugar and total sugar contents.
- the range of the independent variables satisfying all of the pH values, the total acidities, the hydration rates, the dissolution rates, the Ca contents of the calcium powder and the calcium solution, and the reduced sugar and total sugar contents included the calcium content of 17.50- 20.00% and the dextrose content of 6.7-7.8% (see, Table 18).
- a certain preparation condition that is characterized by a calcium content of 18% and a dextrose content of 7.2% was selected within the predicted optimal range for the preparation condition of calcium powder, which was obtained by overlapping of the contour maps for the dependent variables, and its actual effectiveness upon preparation of calcium powder was evaluated.
- the results are given in Tables 19 and 20, below.
- the quality characteristics of the calcium powder that is, the pH values, total acidities, hydration rates and dissolution rates of the calcium powder products according to the preparation conditions, the Ca contents of the calcium powder and the calcium solution and the reduced sugar and total sugar contents were found to be similar to the predicted values by the RSM, thus verifying the deduced regression equations.
- Reprocessed calcium powder products were prepared using three calcium sources according to the obtained optimal condition for the calcium powder preparation, which was the calcium content of 18% and the dextrose content of 7.2%.
- the calcium sources used in this example were the calcium carbonate, aqua calcium and nano calcium, used in Experimental Example 2, and a solvent for the calcium sources was prepared in a volume of 1,000 ml according to the same method as in Experimental Example 5.
- Each calcium source was dissolved in the solvent with stirring at 65 rpm, and the solution was homogenized at 10,000 rpm for 10 min. Subsequently, the solution was spray-dried using a spray-drier (internal temperature: 100°C) .
- the calcium carbonate-reprocessed powder showed the higher Ca content of 229.84 mg/g than the aqua calcium- and nano calcium-reprocessed powders.
- the reprocessed calcium carbonate exhibited the higher Ca content of 2.11% than the reprocessed aqua calcium and nano calcium having a Ca content of 1.45% and 1.07%, respectively. Therefore, these results indicate that the calcium carbonate-reprocessed powder has a higher dissolution rate than the aqua calcium- and nano calcium-reprocessed powders.
- COMPARATIVE EXAMPLE 1 Comparison of qualities of the reprocessed calcium according to the present invention and a commercially available calcium product
- the calcium powder prepared according to the optimal condition was, with respect to qualities, compared with three commercially available calcium products.
- the compared qualities included water content, pH, total acidity, reduced sugar content and Ca content.
- the calcium powder was prepared by reprocessing calcium carbonate according to the optimal condition according to the present invention, and designated as "KJ calcium".
- the qualities of the calcium powder according to the present invention were compared with those of three commercially available calcium products (A, B and C) .
- the results are given in Table 24, below. As shown in Table 24, the conventional calcium products A and B had a water content near to 1%, while the KJ calcium had a water content of 2.11%, that is lower than the conventional calcium product C.
- the pH and total acidity values were measured after each calcium was dissolved in an amount of 5% (w/v) in 1,000 ml of an acetic acid solution with an initial pH of 2.67 and an initial total acidity of 6.40.
- the KJ calcium showed a pH ranging from 3.58 to 4.87, and this pH value was similar to those in the cases of the conventional calcium products A and B but higher than that in the case of the conventional calcium product C. Also, the KJ calcium showed the highest total acidity of 4.56.
- the KJ calcium showed a dissolution rate of 93.27%, while the conventional calcium products A and B displayed a dissolution rate of 73.00% and 80.08%, respectively. These results indicate that the KJ calcium is more effective in solubilization of calcium.
- the dissolution rate of the KJ calcium was similar to that of the conventional calcium C.
- the KJ calcium showed a high hydration rate of 56.30%. The highest hydration rate of 97.40% was observed in the conventional calcium C.
- the KJ calcium showed a lower L value than the conventional calcium products
- the KJ calcium has a poor brightness.
- the KJ calcium has a high b value representing the brown color intensity (see, Table 25) .
- the conventional calcium product A and B showed a high Ca content of over 400 mg/g, while the KJ calcium prepared according to the optimal condition displayed a higher Ca content of 229.84 mg/g than the conventional calcium product C having a Ca content of 160.79 mg/g.
- the KJ calcium was found to have the similar Ca content of 2.11% to the conventional calcium product A having a Ca content of 2.73%.
- EXAMPLE 1 Preparation of calcium liquids using the calcium powder (KJ calcium) prepared in Preparational Example 1 and the conventional calcium products and comparison of qualities of the calcium liquids
- the calcium powder (KJ calcium) prepared in Preparational Example 1 and the conventional calcium products were dissolved in a brewed vinegar with an initial total acidity of 6.5 in various amounts, thus generating calcium liquids. Then, the calcium liquids were evaluated for pH, total acidity, brown color intensity, turbidity, color intensity and dissolution rate. The results are given in Tables 27 to 32.
- the pH value was found to increase with increasing amounts of the calcium sources.
- the KJ calcium liquid showed relatively low pH values in comparison with the calcium carbonate liquid and the aqua calcium liquid.
- the 10% calcium liquid showed the similar pH value of 4.86 to the 4% calcium carbonate and 4% aqua calcium liquids.
- the calcium carbonate and aqua calcium liquids showed an increase until each calcium source was used in an amount of 4%, but showed a decrease when each calcium source was used in an amount of higher than 4%.
- the brown color intensity increased with increasing amounts of the KJ calcium.
- L values decreased with increasing amounts of the KJ calcium, while a and b values increased with increasing amounts of the KJ calcium.
- the KJ calcium prepared according to the present invention was found to the high dissolution rates of over 98% in the broad amounts ranging from 2% to 10% .
- the calcium carbonate and the aqua calcium showed the high dissolution rates of over 95% in amounts of 4% or lower, but displayed the low dissolution rates of 10% to 50%. It is believed that the increased turbidity of the KJ calcium liquid with increasing contents of the KJ calcium resulted from the fact that the KJ calcium has a higher dissolution rate than other calcium sources.
- the KJ calcium rarely affects qualities of solutions added with the KJ calcium. Also, due to its properties of not largely changing the total acidity and the pH of the acetic acid solution, the KJ calcium may be used as a food additive for beverages having a slightly high total acidity, such as juice.
- the solubilized calcium contents increased with increasing amounts of the calcium sources used.
- the highest solubilized calcium content was observed in the calcium carbonate liquid.
- the 10% aqua calcium and calcium carbonate liquids showed the solubilized calcium contents of 1750 mg/100 ml and 1770 mg/100 ml, respectively.
- the 8% or lower KJ calcium liquid was found to have the highest solubilized calcium content of 1910 mg/100 ml. It is believed that these results originate from the solubilization of calcium being affected by the purity of the calcium sources and their dissolution rates in the acetic acid solution.
- the calcium powder (KJ calcium) which has a relatively high dissolution rate in comparison with the aqua calcium and the calcium carbonate, supplied the highest solubilized calcium contents.
- a calcium liquid was prepared using the KJ calcium in an amount of 10% (w/v), based on the results of Example 1.
- the KJ calcium liquid was treated with activated carbon of 0-
- Solubilized calcium contents of the KJ calcium liquid treated with activated carbon according to the amounts of the activated carbon
- the activated carbon-treated KJ calcium liquids were found to contain solubilized calcium in an amount of- 1.82-2.00 g/100 ml. However, in all of the activated carbon-treated KJ calcium liquids, the solubilized calcium contents were found to be slightly lower than that of the KJ calcium liquid not treated with activated carbon (untreated KJ calcium liquid) . In detail, the KJ calcium liquids treated with 0.02% and 0.04% of activated carbon showed a solubilized calcium content of 1.95 g/lOOml, which was similar to that of the untreated KJ calcium liquid.
- the KJ calcium according to the present invention may be applied to preparation of liquid- phased calcium without large changes in its qualities while improving its sensory qualities.
- the activated carbon is preferably used an amount of 0.03% in the secondary processing for production of liquid-phased calcium.
- each of the KJ calcium, aqua calcium and calcium carbonate was dissolved in a brewed vinegar with an initial pH of 2.43, which had been adjusted to a pH of 2 to 10 using IN HCl and 10% NaOH, in an amount of 10% (w/v) .
- the measured quality characteristics are given in Tables 37 to 39.
- the KJ calcium powder showed a higher dissolution rate than the aqua calcium and the calcium carbonate.
- the aqua calcium and the calcium carbonate were found to be rarely dissolved in the pH range of 6 or higher, whereas the KJ calcium displayed dissolution rates of over 90% and over 50% in the pH 2.0 and in the pH ranging from 6 to 10, respectively.
- the KJ calcium is preferably dissolved in a solution with an initial pH of 2.
- calcium liquids were prepared by dissolving for 12 hrs the KJ calcium and calcium carbonate in a brewed vinegar in an amount of 10% and 6%, respectively, filtered and then subjected to a storability test.
- the filtered KJ calcium liquid and calcium carbonate liquid were subjected to cold storage or stored at 37°C, and, at intervals of seven days, evaluated for changes in qualities, that is, pH, total acidity, turbidity and solubilized calcium contents.
- the results are given in Tables 40 to 43, below.
- the KJ calcium liquid showed a pH of 4.75 and a total acidity of 2.23, and thus identified to be significantly changed during storage in pH and total acidity. Also, like to the KJ calcium liquid, the calcium carbonate liquid did not show a significant change during storage in pH and total acidity.
- the KJ calcium liquid showed a calcium content of 2112 mg/100 ml, while the calcium carbonate liquid displayed a calcium content of 1920 mg/100 ml. Such calcium contents were not changed after storage. These results demonstrate that the two calcium liquids are not changed in qualities of these calcium liquids during storage. Therefore, the two calcium liquids are suitable as food additives.
- a calcium liquid was prepared using the calcium powder (KJ calcium) prepared in Preparational Example 1, as follows.
- Calcium liquids as food additives for juice and other general beverages were prepared by dissolving the KJ calcium and calcium carbonate in vinegar, taking into consideration their effects on total activity of beverages and the recommended calcium intake.
- the calcium liquid as a food additive for juice was prepared using the KJ calcium that had been treated with activated carbon to improve its unique bitterness .
- the KJ calcium was used due to its property of only weakly influencing total acidity of a solution when added to the solution in a larger amount than the conventional calcium products.
- the calcium liquid as a food additive for juice was prepared as follows .
- the calcium liquid as a food additive for other general beverages was prepared using calcium carbonate, as well as using phosphoric acid, lactic acid and dextrose to improve its qualities.
- the calcium liquid as a food additive for juice was found to have a Ca content of 1500 mg/100 ml.
- the calcium liquid as a food additive for other general beverage was found to have a pH of 5.03, a total acidity of 1.27, a brown color intensity of 0.11 and a turbidity of 0.018.
- the calcium liquid for general beverage showed an L value (color intensity) of 96.11, an ⁇ a' value (red color intensity) of -1.03 and a ⁇ b' value (brown color intensity) of 6.50.
- the calcium carbonate liquid is preferably used in preparation of beverages that are not affected by changes in total acidity.
- This calcium liquid was found to have a Ca content of 1700 mg/100 ml.
- the absorption rate of the high-content calcium liquid according to the present invention was investigated for six months with 12 healthy volunteers, who were women at the fifty years of age and lived in the Daegu city, Kyungbuk, Korea.
- the subjects were divided into a control group and two calcium-receiving groups I and II, each of which consisted of four women.
- the calcium liquid as a juice additive, prepared in Example 5 was used as a calcium supplement in a mixed form with an herbal extract.
- the calcium-receiving group I was received with two packs of the herbal calcium drink daily, while the calcium- receiving group II was received with three packs of ⁇ the calcium-enriched herbal calcium drink daily.
- the control group was received with two packs of an herbal solution containing the same ingredients as in the herbal calcium drink except for the calcium liquid, in order to exclude psychological factors and the influence of the herbal ingredients contained in the herbal calcium drink.
- a dietary intake survey was carried out using a 24-hour recall method.
- kinds and amounts of foods ingested for 24 hrs on the day before the survey and ingredients of the foods were recorded.
- the resulting records were analyzed using a nutritional evaluation program, CAN-PRO, which was developed by the Nutritional Information Center under the Korean Nutrition Institute.
- Body fat and WHR were calculated by using a body composition analyzer (Inbody 3.0,
- Bone mineral density was measured in the L2 to L4 of the lumber spine using a bone desitometer using a double energy radiation (Hogomic QDR-4500, USA) . Also, the bone mineral density was measured at the calcaneus using a bone densitometer using an ultrasonic wave (Quantative ultrasound bone imaging scanner UBIS 3000, France) .
- the calcium liquid according to the present invention was evaluated for bioavailability in the form of the herbal calcium drink.
- the results are as follows.
- the clinical subjects were first checked for average calcium intake and healthy states by investing their daily dietary intake and body composition.
- the 12 subjects were divided into three groups, and received with the herbal calcium drink or the herbal solution not containing calcium for six months.
- the average age and body composition of the control group and the calcium-receiving groups I and II are given in Table 46, below. Members of each group were selected within the range with no difference between the groups in average age, height, body weight, BMI and body fat.
- the measured daily total calorie intake and calorie intake per nutrient are given in Table 47, below.
- the calcium-receiving group I showed the highest daily total calorie intake of about 1751 Kcal. Daily intake of carbohydrates, proteins and fats was found in similar levels among the groups. All of the subjects did not meet the recommended Korean daily calcium intake. In case of phosphor that plays an important role in the absorption of calcium, the phosphor intake was found to be higher than the calcium intake.
- the excessive phosphor ingestion in comparison with the ingested amount of calcium can reduce the absorption rate of calcium. Based on these results, the twelve subjects were divided into the three groups, each of which consisted of four subjects.
- the bone mineral density measured before and after the clinical test for six months is given in Table 48, below. As shown in Table 48, osteopenia was observed in all of the subjects before the clinical test.
- a normal person has a bone mineral density T-score value of 1
- a T-score value of -1 indicates that a patient has osteopenia
- a T-score value of -2 indicates that a patient has osteoporosis.
- all of the subjects were found to suffer from osteopenia.
- the calcium-receiving group II showed the lowest bone mineral density (BMD) T-score of -1.8.
- BMD bone mineral density
- the calcium liquid-receiving groups I and II showed an increase in BMD or maintained BMD, whereas the control group not administered with the calcium liquid showed a decrease in BMD.
- BUA and SOS measurements were carried out at the calcaneus, and the results are given in the above Table 48.
- the BUA and SOS values decrease as BMD decreases.
- the calcium liquid-receiving groups I and II displayed a mild decrease in BUA and SOS in comparison with the control group.
- the biochemical assay results for the clinical subjects are given in Table 49. All of the subjects were found to have increased levels of serum calcium. However, the calcium liquid-receiving groups I and II showed higher increases in serum calcium than the control group.
- the level of the bone formation marker, osteocalcin typically increases in serum of patients suffering from osteoporosis. Serum osteocalcine levels were elevated in all of the clinical subjects. However, the calcium liquid- receiving groups I and II showed a higher increase in serum osteocalcine levels than the control group (see, Table 49) .
- the level of the bone absorption marker deoxypyridinoline is known to increase in urine of patients suffering from osteoporosis. Urine deoxypyridinoline levels were reduced in all of the clinical subjects. In particular, the calcium liquid-receiving groups I and II showed a higher decrease in urine deoxypyridinoline levels than the control group.
- the present invention provides a solvent capable of increasing solubility of calcium, a calcium powder with enhanced solubility, which is prepared using the solvent, and a calcium liquid prepared using the calcium powder.
- the calcium powder and the calcium liquid can be used as a food additive or as a beverage.
- this ⁇ invention is very useful in the food industry field.
Abstract
Disclosed is a method of preparing a solvent capable of enhancing solubility of calcium. In addition, the present invention discloses a method of preparing a calcium powder with enhanced solubility, based on the dissolution of calcium in the solvent, and a method of preparing a calcium liquid, based on the dissolution of the calcium powder in vinegar.
Description
Method for production of solvent for high solution of calcium, calcium powder with high solubility thereof and calcium liguid thereof
Technical Field
The present invention relates to methods of preparing a solvent for dissolution of calcium, a calcium powder prepared using the solvent, and a calcium liquid prepared using the calcium powder. More particularly, the present invention relates to a method of preparing a solvent capable of enhancing the solubility of calcium, a method of preparing a calcium powder with remarkably enhanced solubility, based on the , dissolution of calcium in the solvent, and a method of preparing a calcium liquid, based on the dissolution of the calcium powder in vinegar.
Background Art
Typically, calcium is a constituent of bone and teeth, and is an inorganic substance involved in various biological reactions, such as enzyme activation, regulation of nervous excitation, muscle contraction and blood clotting. In detail, calcium, which is an essential element for the body, plays critical roles in various biochemical functions of the body, for example, formation of bone and teeth, blood clotting, muscle contractions and relaxation, transmission of nervous signals, regulation of nervous excitation, regulation of permeability of plasma membrane, absorption of vitamin Bχ2,
fusion of plasma membrane and cell division.
On the other hand, osteoporosis has become a severe disease in society. Osteoporosis is caused by decalcification. When calcium loss occurs, bone becomes weak, resulting in the production of the structure like a hornet' s nest. Such decalcified bone is thus weak. Therefore, it is easily fractured, even by daily physical actions, such as lifting of some materials and bending the body. Osteoporosis is generally recognized to commonly occur with advancing age, but can occur even in people with well-regulated hormone balance. Thus, it is very important to prevent the disease.
Therefore, the most effective method to form and maintain strong and healthy bone is to regularly ingest a suitable amount of calcium from early life to advanced life. The moderns ingest a large amount of animal proteins with improved economic welfare. However, the increased intake of animal proteins is known to stimulate calcium excretion
(Johrαson L.A., Alcantara E.N. and Linkswiler H.M., Effect of
Level of Protein Intake on Urinary and Fecal Calcium and Calcium Retention of Young Adult Males. J. Nutr. 100, 1425-1432, 1970; Margen S., Chu J.Y., Kaufman N.A. and Colloway D.H, Studies in calcium metabolism. 1. The calciuretic effect of dietary protein. Am. J. Clin. Nutr. 27, 584-590, 1974.3, 4). In this regard, the moderns are exposed to severe calcium deficiency, and thus, are at high risk for osteoporosis.
According to a national nutrition survey in Korea, the recommended daily amount of calcium is 700 mg for adults (ages 20 and older) and 800-900 mg for juveniles. However, juveniles in Korea were found to ingest about 500-600 mg of calcium, and
not to meet the daily requirement of calcium (the nutrition evaluation part of the report for national health and nutrition survey, the Korean Health & Welfare Ministry, 1999) .
For this reason, the need for calcium supplementation increases, leading to many studies that investigated ways to achieve both quantitative and qualitative intake of calcium. As a result, various calcium products were produced, which include calcium sources with high bioavailability, calcium- enriched foods, calcium supplements and calcium availability- improved substances. However, since calcium has low solubility and low absorption rate in the body, calcium deficiency is not solved simply by ingestion of a large amount of calcium- containing foods. Therefore, strategies capable of improving the solubility and the absorption rate of calcium must be constructed.
However, currently, there is no sufficient report of increasing absorption of calcium into the body. In addition, there are only a few studies into calcium powder and calcium liquid, which have remarkably improved solubility by reprocessing of calcium.
Disclosure of the Invention
Therefore, the present invention aims to provide a method of preparing a solvent capable of producing highly soluble calcium powder, a method of preparing a calcium powder using the solvent, and a method of preparing a calcium liquid using the calcium powder.
To achieve the above objects, the present invention
provides a method of preparing a solvent for dissolution of calcium, including mixing 97.14% (w/w) of apple vinegar with a total acidity of 6.6, 0.2% (w/w) of phosphoric acid, 0.15%
(w/w) of lactic acid, 1.2% (w/w) of a tangle extract and 1.3% (w/w) of a malt extract.
In addition, the present invention provides a method of preparing a highly-soluble reprocessed calcium powder, including adding 17.50-20.00% (w/v) of calcium carbonate and 6.7-7.8% (w/v) of dextrose to the solvent prepared according to the above method, dissolving the calcium carbonate and the dextrose in the solvent, homogenizing the resulting solution and spray-drying the homogenized solution.
Further, the present invention provides a method of preparing a highly-soluble reprocessed calcium liquid, including dissolving the calcium powder prepared according to the immediately above method in a vinegar as a solvent.
Brief Description of the Drawings
The above and other objects, features and other advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction, with the accompanying drawings, in which:
Fig. 1 is a graph showing the ' solubility of aqua calcium in various vinegar solutions;
Fig. 2 is a graph showing the solubility of aqua calcium in an apple vinegar solution A under various initial acidities;
Fig. 3 is a graph showing the solubility of nano calcium in an apple vinegar solution A under various initial acidities;
Fig. 4 is a graph showing the solubility of calcium carbonate in an apple vinegar solution A under various initial acidities;
Fig. 5 is a graph showing the solubility of aqua calcium and calcium carbonate in an apple vinegar solution A;
Fig. 6 is a graph showing the solubility of 2% aqua calcium in various organic acids under various initial acidities;
Fig. 7 is a graph showing the solubility of 3% aqua calcium according to various concentrations of acetic acid and lactic acid;
Fig. 8 is a graph showing the solubility of 3% calcium carbonate according to various concentrations of acetic acid and lactic acid; Fig. 9 is a graph showing the solubility of various calcium types according to concentrations of vinegar;
Fig. 10 is a contour map showing changes in pH of a calcium powder according to contents of calcium and dextrose;
Fig. 11 is a contour map showing changes in total acidity of a calcium powder according to contents of calcium and dextrose;
Fig. 12 is a contour map showing changes in hydration rate of a calcium powder according to contents of calcium and dextrose; Fig. 13 is a contour map showing changes in solubility of a calcium powder according to contents of calcium and dextrose;
Fig. 14 is a contour map showing changes in reduced sugar content of a calcium powder according to contents of
calcium and dextrose;
Fig. 15 is a contour map showing changes in total sugar content of a calcium powder according to contents of calcium and dextrose; Fig. 16 is a contour map showing changes in solubilized calcium content of a calcium powder according to contents of calcium and dextrose;
Fig. 17 is a contour map showing changes in solubilized calcium content of a calcium solution that is prepared by dissolving a calcium powder in an acetic acid solution according to contents of calcium and dextrose; and
Fig. 18 is a graph showing overlapping of the above contour maps for the dependent variables for the preparation of a calcium powder.
Best Mode for Carrying Out the Invention
Calcium is water-insoluble and difficult to add to foods due to its bitterness. Also, because of its poor absorption properties into the body, calcium is mostly excreted. Therefore, in developing calcium products, calcium is urgently required to be improved in solubility and body absorbability.
To facilitate absorption of calcium, calcium-containing foods or pharmaceutical preparations should be first broken down and solubilized in the stomach while ionizing calcium ions. On the other hand, the absorption of calcium is affected by the breakdown rate and solubility of digested calcium diets or supplements. That is, the absorption of calcium increases
as calcium diets or supplements are rapidly broken down and solubilized and as calcium ionization occurs at higher levels.
Keeping in mind the fact that calcium is bio-available and easily absorbed by the body in a soluble and ionized state, the present inventors investigated on solubility of calcium in vinegar solutions, produced a highly soluble calcium powder, based on the above results, and then prepared a calcium liquid capable of being used as a food additive, using the calcium powder.
A highly-soluble calcium powder was first prepared, and a calcium liquid was then prepared using the calcium powder, based on the results of Experimental Examples 1 to 4 of the present invention, as follows. Optimal solubility of calcium in vinegar was investigated by measuring solubility of three calcium types in four vinegar solutions, which are commercially available. Aqua calcium was found to be completely solubilized in all vinegar solutions in an amount of 2.0% (w/v) . In a vinegar solution with an initial total acidity of 2, aqua calcium used in an amount of 2.0% (w/v) concentration showed a similar solubility to that described immediately above, and nano calcium with low purity showed a low solubility. In the same vinegar solution, calcium carbonate displayed a similar solubility to the aqua calcium.
In addition, with respect to saturation solubility of calcium, when aqua calcium and calcium carbonate were added to a vinegar solution with a total acidity of 6.6 in amounts of up to 6% (w/v) , their solubility was greatly increased, whereas
being no longer increased in amounts of higher than 7% (w/v) .
These results indicate that such calcium forms react with organic acids to generate C02 and be solubilized in an ionized form, and that calcium solubility increases with increasing initial total acidity of vinegar and increasing concentration of a calcium source.
On the other hand, the effect of organic acids on the solubility of calcium was analyzed. Among tested organic acids, acetic acid was found to have the highest positive effect on calcium solubility. However, rather than a single organic acid, a mixture of several organic acids was found to dissolve much higher amounts of calcium. The pH value of an acid solution increased with increasing amount of calcium, whereas the total acidity of an acid solution decreased inversely with the amount of calcium.
Therefore, when calcium is ingested along with vinegar, its solubility increases, leading to its effective absorption.
Based on the finding and the results of Experimental Example 5, first, a solvent is prepared by mixing 97.14%% (w/w) of apple vinegar with a total acidity of 6.6, 0.2% (w/w) of phosphoric acid, 0.15% (w/w) of lactic acid, 0.01% (w/w) of citric acid, 1.2% (w/w) of a tangle extract and 1.3% (w/w) of a malt extract. Then, a highly soluble calcium powder is prepared by adding to the solvent 17.50-20.00% (w/v) of calcium carbonate and 6.7-7.8% (w/v) of dextrose, based on the total weight of the solvent, dissolving the calcium carbonate and the dextrose in the solvent, homogenizing resulting solution and spray-drying the homogenized solution.
Vinegar is used as a major ingredient in the solvent for
dissolution of calcium, and phosphoric acid and lactic acid are additionally added to the solvent to supplement the action of the vinegar. The organic acids were selected based on the data from the test for their effect on solubility on calcium. Acetic acid showed the highest positive effect on calcium solubility. However, rather than a single organic acid, a mixture of several organic acids was found to be more effective in solubilizing calcium. Thus, phosphoric acid and lactic acid are used as ingredients of the solvent for the solubilization of calcium.
Herein, in order to regulate pH stability and total acidity of calcium after being spray-dried, phosphoric acid and lactic acid, which have a low volatility and a high gravity, are added to the solvent. Also, an extract of filtrated glycosylated malts (15° Brix) for the removal of the bitterness and a heat-water extract of dried tangles for enrichment of trace elements such as iron, phosphor and magnesium are added to the solvent for dissolution of calcium.
To prepare a highly soluble calcium powder, 17.50-20.00% (w/v) of calcium carbonate and 6.7-7.8% (w/v) of dextrose are added to the solvent.
In the process of preparing a reprocessed calcium powder, the dextrose serves as an excipient for spray-drying of the solvent in which calcium carbonate has been dissolved. The contents of the calcium carbonate and the dextrose are optimal amounts, which are determined by pH, total acidity, hydration rates and solubility of the calcium powder under various conditions, and Ca contents, reduced sugar contents and total sugar contents in the powder and a calcium solution
prepared using the calcium powder.
Herein, among various calcium forms, calcium carbonate and aqua calcium are preferable because of showing a distinct increase in solubility. In the present invention, calcium carbonate is used for the preparation of the calcium powder that is used in the preparation of the calcium liquid.
After the calcium sources and dextrose are added to the solvent, the solvent is stirred to dissolve the added substances while not generating bubbles, and homogenized according to a method commonly used in the art. The resulting solution is spray-dried according to a method commonly used in the art to produce a calcium powder.
The present method of preparing a calcium powder is more advantageous than conventional methods for the solubilization of calcium because bubbles caused by C02 production are generated in a relatively small amount.
On the other hand, the present invention provides a method of preparing a calcium liquid, including dissolving in a vinegar solvent the calcium powder prepared by dissolving calcium carbonate and dextrose in the present solvent.
The vinegar solution used for dissolution of calcium preferably has an initial acidity of 6.5.
In addition, the vinegar solution preferably has a pH of 2, which is the most effective pH value on dissolution of calcium. That is, dissolution of KJ calcium powder is believed to be not greatly affected by the initial pH of a solvent, compared to other calcium forms, but the pH of the solvent is preferably 2 to allow for the calcium liquid to contain calcium of 2500 mg/100 ml or higher.
Preferably, the solvent for preparation of a calcium liquid is a mixture of 91.6298 wt% of breed vinegar with a total acidity of over 6.5, 1.4000 wt% of glucose, 0.3500 wt% of phosphoric acid, 0.3000 wt of lactic acid, 0.1000 wt% of acetic acid, 0.0200 wt% of citric acid, 0.0001 wt% of an antifoamer and 0.0001 wt% of grape flavor.
The calcium powder is preferably dissolved in the vinegar solution in an amount of 10% (w/v) .
Preferably, the calcium liquid is supplemented with activated carbon to improve the unfavorable sensory qualities including the bitterness and burning taste, which are caused by the added calcium. The activated carbon is preferably added in an amount of 0.03% (w/v).
In addition, the calcium powder is preferably added to the vinegar solution in an amount of 10% (w/v) based on the total weight of the vinegar solution. The used amount of the calcium powder was determined taking into overall consideration concentration of calcium dissolved in the solvent, changes in total acidity and pH of the solvent, and the solvent' s brown color intensity, turbidity and color intensity, and the like.
The calcium liquid is preferably filtered to remove impurities according to a method commonly used in the art, and preferably, by a filtration method using diatomaceous earth. After being filtered, the calcium liquid is preferably sterilized using a sterilizer at a high temperature for a very short time.
In an Experimental Example of the present invention, the absorption rate of calcium contained in the calcium liquid was determined by measuring bone mineral density, serum calcium
levels and serum osteocalcin levels in human subjects who have consumed a calcium-enriched herbal pouch drink containing the calcium liquid. Advantageous effects The solvent capable of improving the solubility of calcium, the highly soluble calcium powder prepared using the solvent and the calcium liquid prepared using the calcium powder according to the present invention can be used as a food additive or a beverage, and is thus an useful invention in the food industry.
A better understanding of the present invention may be obtained through the following examples which are set forth to illustrate, but are not to be construed as the limit of the present invention. Also, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims .
EXPERIMENTAL EXAMPLE 1: Evaluation of solubility of calcium in various vinegar solutions
Used in this test were apple vinegar A (Samhan-Saehan Company, total acidity: 6.6) and B (Daehakcheon Company, total acidity: 6.0) and persimmon vinegar C (Samhan-Saehan Company, total acidity: 4.1) and D (Daehakcheon Company, total acidity: 5.8), which are commercially available. 50 ml of each vinegar solution was put into a 100-ml Erlenmeyer flask. Aqua calcium
(34.08% calcium, Bio-DeltaKorea Company) was added to the vinegar solution in various amounts of 0.5%, 1.0%, 1.5% and 2.0% (w/v). After the solution was agitated at 200 rpm at 30°C overnight, the solubility of calcium was analyzed.
The results of the test for the solubility of aqua calcium according to the vinegar types A, B, C and D and the concentrations of aqua calcium, that is, 0.5, 1.0%, 1.5% and 2.0% (w/v), are given in Table 1, below and Fig. 1.
TABLE 1
Changes in pH, total acidity, turbidity and brown color intensity of and residual calcium amount in the vinegar solutions according to the content of aqua calcium
When the aqua calcium with a purity of 34.08% is added in amounts of 0.5% and 2.0%, it can be expressed as "completely solubilized" if the calcium content weights (mg%) are higher
than 170.4 mg% and 681.6 mg%, respectively. As shown in Fig.
1, all of the vinegar solutions were found to completely dissolve aqua calcium in all of the tested amounts of 0.5%, 1.0%, 1.5% and 2.0%.
EXPERIMENTAL EXAMPLE 2: Evaluation of solubility of calcium according to calcium forms
Aqua calcium (34.08% calcium) and nano calcium (20.22% calcium), used in this test, were purchased from the Bio- DeltaKorea Company) and MSC Co. Ltd., respectively. Also, calcium carbonate (49.5% calcium) used as a food additive was used in this test.
After being adjusted to an initial acidity of 2, 4 or 6, 50 ml of the apple vinegar solution A was put into a 100-ml Erlenmeyer flask. Aqua calcium, nano calcium and calcium carbonate were added to the vinegar solution A in various amounts of 0.5%, 1.0%, 2.0% and 3.0% (w/v). After each solution was agitated at 200 rpm at 30°C overnight, the solubility of calcium was analyzed.
(1) Aqua calcium The results of the test for the solubility of aqua calcium according to the initial total acidities (2, 4 and 6) of the vinegar solution A and the concentrations (0.5%, 1.0%, 2.0% and 3.0%, w/v) of aqua calcium are given in Table 2, below, and Fig. 2.
TABLE 2
Changes in pH, total acidity, turbidity and brown color
intensity of and residual calcium amount in the apple vinegar A added with aqua calcium according to the initial acidity of the apple vinegar A
The initial pH value of the vinegar solution decreased with increasing initial total acidity. The pH value increased as calcium was added, like the report described by Shin HS and Kim GH (Effect of preparation conditions of eggshell calcium and organic acids on ionization of calcium, the Journal of Korean Agrichemistry. 40, 531-535, 1997), in which, when eggshell calcium was added to a highly acidic solution in an amount of 1%, the pH of the solution was increased to a highly alkali pH value, and such a strong alkali increased ionization of calcium. When the vinegar solution with an initial total acidity of 2 was added with 3% of aqua calcium, it showed a much lower total acidity than other samples. Turbidity and brown color intensity of the vinegar solutions were found to slightly increase with increasing concentrations of calcium added. Like to the case of the total acidity, the residual
calcium amount increased with increasing concentrations of calcium. The highest residual calcium amount was observed when the vinegar solution with an initial total acidity of 2 was added with 3% or aqua calcium, and this case was found to have reduced calcium solubility.
As shown in Fig. 2, aqua calcium of up to 2.0% was completely dissolved under all of the initial total acidity conditions. The case of adding 3.0% of aqua calcium to the vinegar solution with an initial total acidity of 2 was found to have a similar effect on solubilizaiton of calcium to the case of adding 2.0% of aqua calcium to the same vinegar solution. When 2% of aqua calcium was added to the vinegar solution with an initial total acidity of 4 or 6, over 800 mg% of the added calcium was solubilized. Therefore, when the vinegar solution with an initial total acidity of 4 is added with 2% of aqua calcium, it can dissolve the recommended daily required amount of calcium.
(2) Nano calcium
The results of the test for the solubility of aqua calcium according to the initial total acidities (2, 4 and 6) of the vinegar solution A and the concentrations (0.5%, 1.0%,
2.0% and 3.0%, w/v) of nano calcium are given in Table 3, below, and Fig. 3.
TABLE 3 Changes in pH, total acidity, turbidity and brown color intensity of and residual calcium amount in the apple vinegar A added with nano calcium according to the initial acidity of the apple vinegar A
In the vinegar solutions added with nano calcium, pH and total activity values were found to be similar to those shown in the cases of using aqua calcium, turbidity and brown color intensity increased with increasing concentrations of calcium added. Also, residual calcium amount was found to increase with increasing concentrations of calcium added, leading to a reduction in the solubility of calcium.
As shown in Fig. 3, in all of the samples, solubility of calcium increased with increasing initial total acidity of the
samples. Nano calcium was found to have a lower solubility than aqua calcium in all samples, due to its lower purity than aqua calcium.
(3) Calcium carbonate The results of the test for the solubility of aqua calcium according to the initial total acidities (2, 4 and 6) of the vinegar solution A and the concentrations (0.5%, 1.0%, 2.0% and 3.0%, w/v) of calcium carbonate are given in Table 4, below, and Fig. 4.
TABLE 4
Changes in pH, total acidity, turbidity and brown color intensity of and residual calcium amount in the apple vinegar A added with calcium carbonate according to the initial acidity of the apple vinegar A
When added with 2% and 3% of calcium, the vinegar solution with an initial total acidity of 2 displayed a much
lower total acidity than the case of being added with 0.5% and 1% of calcium, and showed a much lower calcium solubility than the case of being' added with 0.5% and 1% of calcium.
As shown in Fig. 4, when added with 0.5% and 2% of calcium carbonate, all of the vinegar solutions with an initial total acidity of 2, 4 or 6 displayed enhanced solubility of calcium. However, no increase in solubility of calcium was observed when the vinegar solution with an initial total acidity of 2 was added with 3% of calcium carbonate, because total acidity was higher than concentration of calcium. Total acidity increased with increasing concentrations of calcium added. It is believed that, when the calcium concentration is higher than the initial total acidity, total acidity approaches zero, leading to a leveling of solubility of calcium upon additional calcium addition. Also, calcium carbonate was found to be not completely dissolved in all of the vinegar solutions. It is believed that calcium carbonate with a higher purity than aqua calcium or nano calcium can be completely dissolved by employing vinegar with a higher initial total acidity than that in this test. However, calcium carbonate was found to be more effective in solubilization in vinegar than aqua calcium or nano calcium, as follows. Recommended daily calcium intake was obtained in a state of be ionized when only 2% of calcium carbonate was added to the vinegar solution with an initial total acidity of 2.
(4) Saturation solubility of calcium
In order to investigate saturation solubility, of calcium, aqua calcium and calcium carbonate were added to the
vinegar solution A with a total acidity of 6.6 in an amount of 4% to 10% (w/v) . The results are given in Table 5, below, and Fig. 5.
TABLE 5
Changes in pH, total acidity, and residual calcium amount in the apple vinegar A added with aqua calcium and calcium carbonate
In the 4% and 5% calcium concentrations, the vinegar solution A showed higher pH values when added with calcium carbonate than when added with coral carbonate. However, in the calcium concentrations of 6% or higher, the vinegar solution A displayed higher pH values when added with coral carbonate. The pH value was found to increase with increasing concentrations of calcium added. Higher total acidities were observed in the vinegar solution A that had been added with 4% and 5% aqua calcium and with 6% or higher calcium carbonate. Both of the calcium forms displayed similar residual calcium amounts to each other. Solubility of calcium decreased
inversely with concentrations of calcium added.
As shown in Fig. 5, in the vinegar solution A with an initial total acidity of 6.6, aqua calcium of up to 6% was increased in solubility while being completed dissolved. However, only a slight increase in solubility of aqua calcium of 7% or higher was observed. Due to its high purity, calcium carbonate was not completely dissolved in the vinegar solution A with a total acidity of 6.6 in the various amounts used. However, in solubility in the vinegar solution, calcium carbonate displayed a great increase when used in the amounts of up to 6% and a slight increase when used in the amounts of 7% or higher. These results indicate that optimal solubility of calcium according to the initial total acidity of vinegar increases proportionally with the initial total acidity of vinegar and calcium concentrations.
EXPERIMENTAL EXAMPLE 3: Evaluation of solubility of calcium in organic acids
(1) Effect of the kinds of organic acids
In order to investigate the effect of organic acids on solubility of calcium, acetic acid, lactic acid, tartaric acid and citric acid were adjusted to initial total acidities of 2, 4 and 6. Then, 2% (w/v) of aqua calcium was added to 100 ml of each of the organic acids. The test results are given in Table 6, below, and Fig. 6.
TABLE 6
Changes in pH, total acidity, turbidity and brown color intensity of and residual calcium amount in the organic acid
solutions added with aqua calcium according to the kinds and the initial acidity of the solutions
In case of having an initial total acidity of 2, the tartaric acid solution showed the highest pH value, while the acetic acid solution displayed the lowest pH value. In contrast, in case of having an initial total acidity of 6, the acetic acid solution showed the highest pH value, while the tartaric acid solution displayed the lowest pH value. With respect to pH, as the initial total acidity . increases, acetic acid is slightly affected by calcium added, whereas tartaric acid is greatly affected by calcium added. In case of having an initial total acidity of 6, the acetic acid solution showed the highest total acidity, while the lactic acid solution displayed the lowest total acidity. The turbidity and brown color intensity of the organic acid solutions were found to increase with increasing initial total acidity. The residual calcium amount was higher in the tartaric acid and citric acid solutions than the acetic acid and citric acid solutions.
As shown in Fig. 6, solubility of calcium in the acetic
acid and lactic acid solutions was increased in the initial total acidity of up to 4, but slightly increased in the initial total acidity of 6 in comparison with the same solutions with an initial total acidity of 4. Calcium was not dissolved in all of the tartaric acid solutions. In the citric acid solutions, calcium started to dissolve in the initial total acidity of 4, and its solubility was greatly increased in the initial total acidity of 6. In case of having an initial total acidity of 2, among the organic acid solutions, the acetic acid solution dissolved 594.35 mg% of aqua calcium, and thus, showed the highest calcium solubility. The above result in that the vinegar solution with an initial total acidity of 2 dissolved 722.25 mg% of aqua calcium indicates that the organic acids can dissolve higher amounts of calcium when used in combination than when used individually.
(2) Effect of the concentrations of organic acids on solubility of various calcium sources
In order to investigate the effect of organic acids on solubility of calcium according to their concentrations and forms, acetic acid and lactic acid with various total acidities of 1 to 5 were prepared in an amount of 100 ml, and then added with 3% (w/v) of aqua calcium and 3% (w/v) of calcium carbonate. The test results are given in Tables 7 and 8, below, and Figs. 7 and 8.
TABLE 7
Changes in pH, total acidity, turbidity and brown color intensity of and residual calcium amount in the acetic acid and lactic acid solutions added with 3% (w/v) of aqua calcium according to the kinds and the initial acidity of the solutions
TABLE 8
Changes in pH, total acidity, turbidity and brown color intensity of and residual calcium amount in the acetic acid and lactic acid solutions added with 3% (w/v) of calcium carbonate according to the kinds and the initial acidity of the solutions
When added with aqua calcium, under the initial total acidities of up to 2, the acetic acid solutions showed higher pH values than the lactic acid solutions. The total acidity was found to increase with increasing initial acidity of the organic acid solutions. The brown color intensity of the organic acid solutions increased with increasing total acidity thereof. The solubility of both aqua calcium and calcium
carbonate was found to increase with increasing initial total acidity of the acetic acid and lactic acid solutions. As concentrations of the organic acids increased, the organic acids increasingly reacted with calcium, resulting in an increase in calcium solubility and a decrease in total acidity of the organic acid solutions.
As shown in Figs. 7 and 8, the solubility of aqua calcium and calcium carbonate was higher in the acetic acid solutions in all of the test conditions than the lactic acid solutions. The calcium solubility was found to increase with increasing concentrations of organic acids.
EXPERIMENTAL EXAMPLE 4: Evaluation of the effect of vinegar concentration (acidity) on solubility of calcium
In order to investigate the effect of vinegar concentration (acidity) on solubility of calcium, the commercially available apple vinegar A was diluted with various concentrations of 0, 20, 40, 60, 80 and 100% (v/v) in a volume of 100 ml. Then, aqua calcium, nano calcium and calcium carbonate were added to each of the apple vinegar solutions in an amount of 3% (w/v) . The test results are given in Table 9, below, and Fig. 9.
TABLE 9
Changes in pH, total acidity, turbidity and brown color intensity of and residual calcium amount in the apple vinegar solutions added with aqua calcium, nano calcium or calcium carbonate according to the concentrations of vinegar
The apple vinegar solution A displayed higher pH values when added with aqua calcium than when added with nano calcium or calcium carbonate. The pH values decreased with increasing concentrations of vinegar. In all of the cases of being added with three calcium sources, there was no large change in total acidity in the vinegar solutions with a vinegar concentration of 0% or 20%. However, the total acidity was greatly increased in the vinegar solutions with a vinegar concentration of 40% or higher.
As shown in Fig. 9, aqua calcium was completely solubilized in the 60% vinegar solution, while nano calcium was completely solubilized in the 40% vinegar solution. Solubility of aqua calcium and nano calcium were slightly increased in the vinegar solutions with a vinegar concentration higher than 60%
or 40%. Calcium carbonate was found to be completely not solubilized in all of the vinegar solutions, but to be solubilized increasing with the vinegar concentrations.
EXPERIMENTAL EXAMPLE 5: Investigation of optimal conditions for preparation of calcium powder
The calcium carbonate (calcium content: 48.9% capable of being used as a food additive) , used in Experimental Example 2, was used in this test. A solvent used in this test was prepared by mixing the apple vinegar solution A used in Experimental Example 1, phosphoric acid, lactic acid, citric acid, a tangle extract and a malt extract in a ratio of 97.14%,
0.2%, 0.15%, 0.01%, 1.2% or 1.3% (v/v) with a volume of 100 ml.
The tangle extract was prepared by an extraction method commonly used in the art, and the malt extract (15° Brix) was prepared by glycosylation at 60°C for 6 hrs.
In order to establish the optimal conditions for preparation of calcium powder, a response surface methodology
(RSM) was used. An experimental design of factor variables based on a central composite design was performed as follows. Factors recognized as critical variables in the process of preparing calcium powder, as shown in Table 10, below, that is, calcium content (5% to 25% (w/v) and dextrose content (0% to 20% (w/v) were designated as five grades. Independent variables (conditions for preparation of calcium powder) shown in Table 10 were set as 10 cases, as shown in Table 11, below, according to the central composite design.
TABLE 10 Experimental design for conditions of preparation of calcium powder
TABLE 11
Central composite design for establishment of the optimal condition of calcium powder preparation
Herein, a solvent for calcium was prepared by mixing without generation of bubbles a brewed vinegar, phosphoric acid, lactic acid, citric acid, a tangle extract and a malt extract. Dependent variables affected by the factor variables, that is, quality factors of the calcium powder, including water content (Yi) , pH (Y2) , color intensity (Y4) , brown color intensity (Y5) , hydration rate (Yg) , dissolution rate (Y) , reduced sugar content (Yg) , total sugar content (Yg) , Ca content (Yχo) of the calcium powder and Ca content (Yn) of a calcium solution prepared using the calcium powder, were measured in independent three experiments, and their mean values were used in a regression analysis.
A prediction by the regression analysis was performed with a SAS (statistical analysis system) program. When a
critical point was not a maximum point or a minimum point but a saddle point as a result of the regression analysis, an optimal point was estimated by a ridge analysis, and the optimal condition for preparation of the calcium powder was analyzed by contour map and 3-D response surface analysis.
A calcium powder was prepared by dispersing calcium carbonate and dextrose in various amounts as listed in Table 11 in the solvent and then stirring the solution for dissolution of the calcium carbonate and dextrose at 20°C for 12 hrs. A homogenizer was used to homogenize the particles. The homogenized solution was spray-dried in a spray-drier under predetermined conditions, thus yielding a calcium powder.
The quality of the calcium powder was analyzed in a powder form (hereinafter referred to simply as "calcium powder") and in a liquid form (hereinafter referred to simply as "calcium solution") . A calcium solution in the liquid form was prepared by adding the calcium powder to an acetic acid solution in an amount of 5% (w/v) , agitating the mixture at 200 rpm for 30°C overnight to allow for the calcium powder to be dissolved in the acetic acid solution, and filtering the resulting mixture twice.
The water content of the calcium powder and the calcium solution was measured three times, based on the Korean food standard code. The color intensity (Hunter' s color) of each of the calcium powders, prepared according to the ten cases shown in Table 11, was measured using a colorimeter (CR-10, Minolta co., Japan). The Hunter's color and brown color intensity of each calcium solution was analyzed using an UV- spectrophotometer.
The hydration rate was measured by dissolving 1% (w/v) of the calcium powder in distilled water, filtering the solution with a filter, measuring the weight of the calcium remained on the filter, and expressing the content of calcium dissolved in the distilled water as %. That is, % hydration was calculated according to the following equation: (the weight of calcium powder before dissolution - the weight of calcium remained on a filter after dissolution) /the weight of calcium powder before dissolution x 100. The dissolution rate was measured by passing each calcium solution through a pre-weighed filter, measuring the weight of calcium remained on the filter, and expressing the content of calcium dissolved in the acetic acid solution as %. That is, % hydration was calculated according to the following equation: (the weight of calcium powder before dissolution - the weight of calcium remained on a filter after dissolution) /the weight of calcium powder before dissolution x 100.
The reduced sugar - content was measured by a DNS method after diluting the calcium solution. Total sugar content was measured according to the same method as in the measurement of the reduced sugar content after adding 20 ml of the calcium solution to 6N HCl to decompose calcium.
The Ca content of the calcium powder was measured by incinerating a predetermined amount of the calcium powder, decomposing the calcium powder in 6N HCl and subjecting suitably diluted samples to analysis of Ca content using AAS (atomic absorption spectrometry) .
The Ca content of the calcium solution was measured by
AAS after the calcium solution was suitably diluted.
The optimal condition for preparation of the calcium powder was predicted within an overlapped region when contour maps for the quality factors were overlapped.
The calcium powder products, prepared according to the 10 cases determined by the central composite design, were evaluated for water content, pH values and total acidity, and the results are given in Table 12, below. Also, the calcium powder products were evaluated for hydration rates, dissolution rates and color intensities. The results are given in Table 13, below. Further, the calcium powder products were evaluated for Hunter7 s color and brown color intensity, and the results are given in Table 14, below.
TABLE 12 Water content, pH and total acidity of the calcium powder products
TABLE 13 Hydration rate, dissolution rate and Hunter' s color of the calcium powder products
TABLE 14 Hunter7 s color and brown color intensity of the calcium powder products
In addition, the measured Ca, reduced sugar and total sugar contents of the calcium powder products and the- Ca content of the calcium solution are summarized in Table 15,' below.
TABLE 15 Ca content, reduced sugar content and total sugar content of the calcium powder products
Using the obtained data, a response surface regression analysis was performed to obtain a regression equation for each of the dependent (reaction) variables. The results are given in Table 16, below.
TABLE 16 Regression equations for the quality factors, analyzed by a RSM program
TABLE 17
Optimal conditions for preparation of calcium powder and quality characteristic values per each variable
(1) The water content of each of the calcium powder products prepared by the central composite design is given in the above Table 12, As shown in Table 12, each calcium powder was found to contain water of 2-5%. These results indicate that the calcium powder was not affected greatly by the concentrations of calcium and dextrose.
(2) The regression equations for the pH and total acidity of each calcium powder according to the preparation conditions are given in the above Table 16 and Figs. 10 and 11. R2 values of the regression equations for the pH and the total acidity were found to be 0.9823 and 0.9828 at the significance
level of below 5%. The optimal conditions for preparation of calcium powder are given in the above Table 17. Since the predicted stationary point was a saddle point, a ridge analysis was performed. As a result, the calcium powder preparation condition for the pH variable was the calcium content of 20.32% and the dextrose content of 1.54%. The calcium powder preparation condition for the total acidity variable was the calcium content of 5.03% and the dextrose content of 9.29%. As shown in the contour maps for the pH and the total acidity per preparation condition, both the pH and the total acidity variables were not affected by the dextrose content, but affected by the calcium content.
(3) The hydration rate and the dissolution rate for each of the calcium powder products are given in the above Table 13, and the optimal condition for preparation of calcium powder and contour maps for the hydration rate and dissolution rate are given in the above Table 17 and Figs. 12 and 13, respectively. Also, R2 values of the regression equations for the hydration rate and the dissolution rate were, as shown in Table 16, 0.9975 and 0.8920 at the significance level of below 1% and below 5%, respectively.
(4) As shown in the Tables 13 and 14, in which the color intensity of each calcium powder and the color intensity and the brown color intensity of the calcium solution are given, there was no large change in the Hunter7 s color of the calcium powder. However, the Hunter7 s color of the brown color intensity of the calcium solution was slightly changed according to its preparation condition. These results originated from the difference in the contents of calcium and
dextrose of the calcium powder.
(5) The reduced sugar and total sugar contents of the calcium powder products are given in the above Table 15 and Figs. 14 and 15. Also, R2 values of the regression equations for the reduced sugar content and the total sugar content were, as shown in Table 15, 0.9764 and 0.8731 at the significance level of below 5% and below 10%, respectively. As shown in the contour maps for the reduced sugar and the total sugar, the sugar content increased with increasing dextrose contents. The optimal condition for preparation of calcium powder by the reduced sugar and total sugar variables was similar to that obtained from the hydration rate and dissolution rate variables. These results indicate that the hydration rate, dissolution rate, reduced sugar and total sugar variables are affected by the dextrose content upon the preparation of calcium powder.
(6) The Ca contents of the calcium powder and the calcium solution, prepared by the central composite design, are given in the above Table 15. Response surface regression equations and contour maps, which were obtained using the data in Table 15, are given in the above Table 16 and Figs. 16 and 17. R2 values of the regression equations for the Ca contents of the calcium powder and the calcium solution were 0.9973 and 0.9843 at the significance level of below 1%. The optimal condition for the calcium powder preparation according to the Ca Content is given in the above Table 17. Since the predicted stationary point was a saddle point, a ridge analysis was performed. As a result, the Ca contents of the calcium powder and the calcium solution were 372.38 mg/g and 2.96%,
respectively. The calcium powder preparation condition was the calcium content of 19.22% and the dextrose content of
0.94%. Also, the calcium powder preparation condition to achieve the maximum Ca content in a calcium solution was the calcium content of 19.39% and the dextrose content of 1.02%.
In order to optimize the preparation condition of calcium powder, the optimal range for the calcium powder preparation condition was predicted by overlapping the contour maps for the pH, total acidity, hydration rate and dissolution rate of the calcium powder products according to the preparation conditions, the Ca contents of the calcium powder and the calcium solution, and the reduced sugar and total sugar contents. As shown in Fig. 14, the range of the independent variables satisfying all of the pH values, the total acidities, the hydration rates, the dissolution rates, the Ca contents of the calcium powder and the calcium solution, and the reduced sugar and total sugar contents, which was designated as a slash-marked region, included the calcium content of 17.50- 20.00% and the dextrose content of 6.7-7.8% (see, Table 18).
TABLE 18
Predicted optimal range for the preparation condition of calcium powder by overlapping of the contour maps for the dependent variables
On the other hand, a certain point was selected within ' the predicted range and introduced into the regression equation. Then, the resulting predicted optimal value was
intended to be corroborated.
A certain preparation condition that is characterized by a calcium content of 18% and a dextrose content of 7.2% was selected within the predicted optimal range for the preparation condition of calcium powder, which was obtained by overlapping of the contour maps for the dependent variables, and its actual effectiveness upon preparation of calcium powder was evaluated. The results are given in Tables 19 and 20, below. As shown in Tables 19 and 20, the quality characteristics of the calcium powder, that is, the pH values, total acidities, hydration rates and dissolution rates of the calcium powder products according to the preparation conditions, the Ca contents of the calcium powder and the calcium solution and the reduced sugar and total sugar contents were found to be similar to the predicted values by the RSM, thus verifying the deduced regression equations.
TABLE 19
Predicted values and actual values of qualities (dependent variables) in a certain condition within the preparation condition of calcium powder
TABLE 20
Predicted values and actual values of qualities (dependent variables) in a certain condition within the preparation condition of calcium powder
Preparation Reduced sugar Total sugar Ca content of Ca content of
PREPARATION EXAMPLE 1: Preparation of calcium powder according to the optimal condition
Reprocessed calcium powder products were prepared using three calcium sources according to the obtained optimal condition for the calcium powder preparation, which was the calcium content of 18% and the dextrose content of 7.2%. The calcium sources used in this example were the calcium carbonate, aqua calcium and nano calcium, used in Experimental Example 2, and a solvent for the calcium sources was prepared in a volume of 1,000 ml according to the same method as in Experimental Example 5. Each calcium source was dissolved in the solvent with stirring at 65 rpm, and the solution was homogenized at 10,000 rpm for 10 min. Subsequently, the solution was spray-dried using a spray-drier (internal temperature: 100°C) .
Qualities of the resulting reprocessed calcium products, prepared according to the optimal condition for the calcium powder preparation using calcium carbonate, aqua calcium and nano calcium, are given in Tables 21 to 23, below.
TABLE 21
Qualities (water content, pH, total acidity, dissolution rate and hydration rate) of the calcium products reprocessed according to the optimal condition of the present invention
TABLE 22
Qualities (color intensity and brown color intensity) of the calcium products reprocessed according to the optimal condition of the present invention
TABLE 23
Quality (calcium content) of the calcium products reprocessed according to the optimal condition of the present invention
As shown in Table 21, there was no significant difference in the water content and the pH. The calcium carbonate-reprocessed powder showed a total acidity of 4.56, which was lower than that of the powders prepared using aqua calcium and nano calcium. Also, there was no significant difference between the calcium powders in the dissolution rate. The highest hydration rate of 87.76% was observed in the nano calcium-reprocessed powder. The calcium carbonate-reprocessed powder displayed relatively lower Huntex7 s color values and brown color intensity.
The measured Ca contents of the reprocessed calcium products in the powder form or in the form of being dissolved in an acetic acid solution are summarized in the above Table
23. In the powder form, the calcium carbonate-reprocessed powder showed the higher Ca content of 229.84 mg/g than the aqua calcium- and nano calcium-reprocessed powders. In the form dissolved in acetic acid, the reprocessed calcium carbonate exhibited the higher Ca content of 2.11% than the reprocessed aqua calcium and nano calcium having a Ca content of 1.45% and 1.07%, respectively. Therefore, these results indicate that the calcium carbonate-reprocessed powder has a higher dissolution rate than the aqua calcium- and nano calcium-reprocessed powders.
COMPARATIVE EXAMPLE 1: Comparison of qualities of the reprocessed calcium according to the present invention and a commercially available calcium product
The calcium powder prepared according to the optimal condition was, with respect to qualities, compared with three commercially available calcium products. The compared qualities included water content, pH, total acidity, reduced sugar content and Ca content. The calcium powder was prepared by reprocessing calcium carbonate according to the optimal condition according to the present invention, and designated as "KJ calcium". The qualities of the calcium powder according to the present invention were compared with those of three commercially available calcium products (A, B and C) . The
results are given in Table 24, below. As shown in Table 24, the conventional calcium products A and B had a water content near to 1%, while the KJ calcium had a water content of 2.11%, that is lower than the conventional calcium product C.
TABLE 24 Comparison of qualities of the KJ calcium and the conventional calcium products
The pH and total acidity values were measured after each calcium was dissolved in an amount of 5% (w/v) in 1,000 ml of an acetic acid solution with an initial pH of 2.67 and an initial total acidity of 6.40. The KJ calcium showed a pH ranging from 3.58 to 4.87, and this pH value was similar to those in the cases of the conventional calcium products A and B but higher than that in the case of the conventional calcium product C. Also, the KJ calcium showed the highest total acidity of 4.56.
The KJ calcium showed a dissolution rate of 93.27%, while the conventional calcium products A and B displayed a dissolution rate of 73.00% and 80.08%, respectively. These results indicate that the KJ calcium is more effective in solubilization of calcium. The dissolution rate of the KJ calcium was similar to that of the conventional calcium C. In
addition, the KJ calcium showed a high hydration rate of 56.30%. The highest hydration rate of 97.40% was observed in the conventional calcium C.
With respect to the color intensity, the KJ calcium showed a lower L value than the conventional calcium products
A, B and C, indicating that the KJ calcium has a poor brightness. In addition, the KJ calcium has a high b value representing the brown color intensity (see, Table 25) .
TABLE 25 Comparison of qualities of the KJ calcium and the conventional calcium products
TABLE 26 Comparison of qualities of the KJ calcium and the conventional calcium products
In the powder form, the conventional calcium product A and B showed a high Ca content of over 400 mg/g, while the KJ calcium prepared according to the optimal condition displayed a higher Ca content of 229.84 mg/g than the conventional calcium
product C having a Ca content of 160.79 mg/g. However, in the form of being dissolved in the acetic acid solution, the KJ calcium was found to have the similar Ca content of 2.11% to the conventional calcium product A having a Ca content of 2.73%. These results indicate that the KJ calcium with a lower purity than the conventional calcium A is more effective in solubilization of calcium than the conventional calcium A.
EXAMPLE 1: Preparation of calcium liquids using the calcium powder (KJ calcium) prepared in Preparational Example 1 and the conventional calcium products and comparison of qualities of the calcium liquids
The calcium powder (KJ calcium) prepared in Preparational Example 1 and the conventional calcium products were dissolved in a brewed vinegar with an initial total acidity of 6.5 in various amounts, thus generating calcium liquids. Then, the calcium liquids were evaluated for pH, total acidity, brown color intensity, turbidity, color intensity and dissolution rate. The results are given in Tables 27 to 32.
TABLE 27 Changes in pH of the calcium liquids
TABLE 28
Changes in total acidity of the calcium liquids
TABLE 29 Brown color intensity of the calcium liquids
TABLE 30 Turbidity of the calcium liquids
TABLE 31 Hunter7 s color of the calcium liquids
TABLE 32 Dissolution rates of the calcium liquids
In all of the calcium liquids, the pH value was found to increase with increasing amounts of the calcium sources. However, the KJ calcium liquid showed relatively low pH values in comparison with the calcium carbonate liquid and the aqua calcium liquid. The 10% calcium liquid showed the similar pH value of 4.86 to the 4% calcium carbonate and 4% aqua calcium liquids.
The addition of the KJ calcium to the acetic acid solution with the initial total acidity of 6.5 (the KJ calcium liquid) resulted in a decrease in total acidity to the range of 5.99 to 1.94. However, such a decrease in total acidity of the KJ calcium liquid was found to occur in lower levels than the calcium carbonate and aqua calcium liquids, which had a total acidity of 4.53 to 0.08. These results indicate that the KJ calcium liquid is more effective in storing foods and maintaining qualities of foods than the calcium carbonate and aqua calcium liquids and does not negatively affect sensory qualities of foods.
With respect to the brown color intensity, the calcium carbonate and aqua calcium liquids showed an increase until each calcium source was used in an amount of 4%, but showed a decrease when each calcium source was used in an amount of higher than 4%. In the KJ calcium liquid, the brown color intensity increased with increasing amounts of the KJ calcium. In addition, there was no large change in color intensity according to the used amounts of the calcium carbonate and aqua calcium. However, in the KJ calcium liquid, L values decreased
with increasing amounts of the KJ calcium, while a and b values increased with increasing amounts of the KJ calcium.
With respect to the turbidity, a gradual increase with increasing amounts of the KJ calcium was observed. However, there was no change in turbidity of the calcium carbonate and aqua calcium liquids. With respect to the dissolution rate in the acetic acid solution, the KJ calcium prepared according to the present invention was found to the high dissolution rates of over 98% in the broad amounts ranging from 2% to 10% . In contrast, the calcium carbonate and the aqua calcium showed the high dissolution rates of over 95% in amounts of 4% or lower, but displayed the low dissolution rates of 10% to 50%. It is believed that the increased turbidity of the KJ calcium liquid with increasing contents of the KJ calcium resulted from the fact that the KJ calcium has a higher dissolution rate than other calcium sources.
Therefore, it is believed that the KJ calcium rarely affects qualities of solutions added with the KJ calcium. Also, due to its properties of not largely changing the total acidity and the pH of the acetic acid solution, the KJ calcium may be used as a food additive for beverages having a slightly high total acidity, such as juice.
The measured contents of solubilized calcium in the calcium liquids are given in Table 33.
TABLE 33
Solubilized calcium contents in the calcium liquids
In all of the calcium liquids, the solubilized calcium contents increased with increasing amounts of the calcium sources used. The highest solubilized calcium content was observed in the calcium carbonate liquid. However, the 10% aqua calcium and calcium carbonate liquids showed the solubilized calcium contents of 1750 mg/100 ml and 1770 mg/100 ml, respectively. The 8% or lower KJ calcium liquid was found to have the highest solubilized calcium content of 1910 mg/100 ml. It is believed that these results originate from the solubilization of calcium being affected by the purity of the calcium sources and their dissolution rates in the acetic acid solution. When used in an amount of 10%, the calcium powder (KJ calcium) , which has a relatively high dissolution rate in comparison with the aqua calcium and the calcium carbonate, supplied the highest solubilized calcium contents.
EXAMPLE 2: Preparation of calcium liquid treated with activated carbon
A calcium liquid was prepared using the KJ calcium in an amount of 10% (w/v), based on the results of Example 1. In order to improve the unfavorable sensory qualities including bitterness and burning taste of the prepared calcium liquid, the KJ calcium liquid was treated with activated carbon of 0-
0.05% (w/v). Then, the KJ calcium liquid was evaluated for pH, total acidity, turbidity, brown color intensity, color
intensity and solubilized calcium contents. The results are given in Tables 34 to 36.
TABLE 34 Changes in pH, total acidity and turbidity of the KJ calcium liquid treated with activated carbon according to the amounts of the activated carbon
, TABLE 35 Changes in brown color intensity and color intensity of the KJ calcium liquid treated with activated carbon according to the amounts of the activated carbon
TABLE 36
Solubilized calcium contents of the KJ calcium liquid treated with activated carbon according to the amounts of the activated carbon
With respect to pH and total acidity, there was no
significant difference between the KJ calcium liquids of being treated with activated carbon or not. Also, the turbidity of the KJ calcium liquid was rarely changed when treated with the activated carbon of up to 0.02%, and slightly increased with increasing amounts of the activated carbon in the range of higher than 0.02%.
Similar to the pH and total acidity, there was no significant difference in brown color intensity and color intensity between the KJ calcium liquids treated with the various amounts of activated carbon.
In addition, the activated carbon-treated KJ calcium liquids were found to contain solubilized calcium in an amount of- 1.82-2.00 g/100 ml. However, in all of the activated carbon-treated KJ calcium liquids, the solubilized calcium contents were found to be slightly lower than that of the KJ calcium liquid not treated with activated carbon (untreated KJ calcium liquid) . In detail, the KJ calcium liquids treated with 0.02% and 0.04% of activated carbon showed a solubilized calcium content of 1.95 g/lOOml, which was similar to that of the untreated KJ calcium liquid.
Based on these results, the KJ calcium according to the present invention may be applied to preparation of liquid- phased calcium without large changes in its qualities while improving its sensory qualities. Herein, with regard to cost, the activated carbon is preferably used an amount of 0.03% in the secondary processing for production of liquid-phased calcium.
EXAMPLE 3: Preparation of calcium liquids with various pH
values
In order to investigate the effect of pH on calcium liquids, each of the KJ calcium, aqua calcium and calcium carbonate was dissolved in a brewed vinegar with an initial pH of 2.43, which had been adjusted to a pH of 2 to 10 using IN HCl and 10% NaOH, in an amount of 10% (w/v) . The measured quality characteristics are given in Tables 37 to 39.
TABLE 37 Dissolution rates of the calcium sources in vinegar according to pH
TABLE 38
Changes in turbidity of the vinegar solutions added with the calcium sources in vinegar according to pH
TABLE 39 Solubilized Ca contents of the vinegar solutions added with the calcium sources according to pH
In all of the calcium sources, their dissolution rates in the vinegar solution decreased with increasing pH. Herein, the KJ calcium powder showed a higher dissolution rate than the aqua calcium and the calcium carbonate. In particular, the aqua calcium and the calcium carbonate were found to be rarely dissolved in the pH range of 6 or higher, whereas the KJ calcium displayed dissolution rates of over 90% and over 50% in the pH 2.0 and in the pH ranging from 6 to 10, respectively.
There was no significant change in turbidity except for the case of dissolving the KJ calcium in the vinegar solution of pH 2.0. The solubilized calcium content decreased with increasing pH. In all of the cases of being added with the calcium sources, the vinegar solution of pH 2.0 showed a solubilized calcium content of over 2000 mg/100 ml. In particular, when added with the KJ calcium, the vinegar solution showed the highest calcium content.
The result in that the vinegar solution showed higher calcium contents when added with the KJ calcium than when added with other calcium sources is believed to result from that the KJ calcium is, although having a lower purity, more effective in solubilization of calcium than the aqua calcium and the calcium carbonate.
These results indicate that the dissolution of KJ calcium in a solution is not relatively largely affected by the initial pH of the solution in comparison with the conventional calcium sources. Also, in order to prepare a calcium liquid containing calcium of over 2500 mg/lOOml, the KJ calcium is
preferably dissolved in a solution with an initial pH of 2.
EXPERIMENTAL EXAMPLE 6: Evaluation of storability of the calcium liquids
Based on the results of the preparation of the calcium liquids, calcium liquids were prepared by dissolving for 12 hrs the KJ calcium and calcium carbonate in a brewed vinegar in an amount of 10% and 6%, respectively, filtered and then subjected to a storability test. In brief, the filtered KJ calcium liquid and calcium carbonate liquid were subjected to cold storage or stored at 37°C, and, at intervals of seven days, evaluated for changes in qualities, that is, pH, total acidity, turbidity and solubilized calcium contents. The results are given in Tables 40 to 43, below.
TABLE 40 Changes in pH of the calcium liquids according to the storage conditions
TABLE 41 Changes in total acidity of the calcium liquids according to the storage conditions
TABLE 42 Changes in turbidity of the calcium liquids according to the storage conditions
TABLE 43 Solubilized calcium contents of the calcium liquids
There was a difference in pH and total acidity during storage between the calcium liquids that had been prepared using the brewed vinegar with an initial pH of 2.35 and an initial total acidity of 6.61. The KJ calcium liquid showed a pH of 4.75 and a total acidity of 2.23, and thus identified to be significantly changed during storage in pH and total acidity. Also, like to the KJ calcium liquid, the calcium carbonate liquid did not show a significant change during storage in pH and total acidity.
With respect to turbidity representing the production of
precipitates during storage, there was no significant difference between before and after the storage (the cold storage and the storage at 37°C) . Visual precipitates were observed during storage at 37°C, but rarely generated during cold storage.
In addition, before storage, the KJ calcium liquid showed a calcium content of 2112 mg/100 ml, while the calcium carbonate liquid displayed a calcium content of 1920 mg/100 ml. Such calcium contents were not changed after storage. These results demonstrate that the two calcium liquids are not changed in qualities of these calcium liquids during storage. Therefore, the two calcium liquids are suitable as food additives.
EXAMPLE 4: Preparation of a calcium liquid using the calcium powder prepared in Preparational Example 1
A calcium liquid was prepared using the calcium powder (KJ calcium) prepared in Preparational Example 1, as follows.
After mixing in a tank 91.6298 g of a brewed vinegar with a total acidity of 6.5, 1.4000 g of glucose, 0.3500 g of phosphoric acid, 0.3000 g of lactic acid, 0.1000 g of acetic acid, 0.0200 g of citric acid, 0.0001 g of an antifoamer and 0.0001 g of grape flavor, 6.2000 g of the calcium powder (KJ calcium) prepared in Preparational Example 1 was dissolved in the mixture with stirring at a low speed for 12 hrs. Then, the resulting solution was subjected to a filtration process using diatomaceous earth to remove impurities. The filtrate was then sterilized using a
sterilizer at a high temperature for a very short time.
EXAMPLE 5: Preparation of calcium liquids as food additives for juice and other general beverages
Calcium liquids as food additives for juice and other general beverages were prepared by dissolving the KJ calcium and calcium carbonate in vinegar, taking into consideration their effects on total activity of beverages and the recommended calcium intake.
The calcium liquid as a food additive for juice was prepared using the KJ calcium that had been treated with activated carbon to improve its unique bitterness . The KJ calcium was used due to its property of only weakly influencing total acidity of a solution when added to the solution in a larger amount than the conventional calcium products. The calcium liquid as a food additive for juice was prepared as follows .
First, 10 g of the calcium powder (KJ calcium) prepared in Preparational Example 1 was dissolved in 100 ml of a brewed vinegar with a total acidity of 6.5 with stirring at 200 rpm at 30°C for 12 hrs, and then filtered with diatomaceous earth twice. The filtrate was treated with activated carbon with stirring at 200 rpm at 30°C for 2 hrs, and then filtered with diatomaceous earth twice. Subsequently, the secondary filtrate was sterilized at 95°C for 10 in, thus generating a highly soluble, reprocessed calcium liquid usable as a food additive for juice.
The calcium liquid as a food additive for other general
beverages was prepared using calcium carbonate, as well as using phosphoric acid, lactic acid and dextrose to improve its qualities.
First, 6 g of calcium carbonate containing calcium with a calcium content of 49.5%, 0.02 g of phosphoric acid, 0.15 g of lactic acid and 0.1 g of dextrose were dissolved in 100 ml of a brewed vinegar with a total acidity of 6.5 with stirring at 200 rpm at 30°C for 12 hrs, and then filtered with diatomaceous earth twice. Subsequently, the secondary filtrate was sterilized at 95°C for 10 min, thus generating a calcium liquid usable as a food additive for general beverages.
The measured qualities of the calcium liquids as food additives for juice and other general beverages are given in Table 44, below.
TABLE 44
Qualities of the calcium liquids as food additives for juice and other general beverages
The calcium liquid as a food additive for juice was found to have a Ca content of 1500 mg/100 ml. The calcium liquid as a food additive for other general beverage was found to have a pH of 5.03, a total acidity of 1.27, a brown color intensity of 0.11 and a turbidity of 0.018. Also, the calcium liquid for general beverage showed an L value (color intensity) of 96.11, an λa' value (red color intensity) of -1.03 and a λb'
value (brown color intensity) of 6.50.
Based on these results, the calcium carbonate liquid is preferably used in preparation of beverages that are not affected by changes in total acidity. This calcium liquid was found to have a Ca content of 1700 mg/100 ml.
These days, calcium-enriched or high-content calcium juices or other general beverages are commercially available. This tendency represents an increased interest for health foods and an increased requirement for calcium intake. In this regard, the calcium liquids were added to a commercially available juice, and the juice was evaluated for changes in qualities and compared with the cases of being added with other calcium sources (Table 45) .
TABLE 45 Changes in pH and total acidity of juices added with the calcium liquid according to the present invention and other calcium sources
When added with calcium lactate that are currently widely used as a food additive for the enrichment of calcium, the orange juice and the grape juice did not show a significant change in their qualities in all of the tested conditions, regardless of the added amounts of the calcium sources and the incubation time. For this reason, calcium lactate is believed to be used as a food additive for juices. When introduced into the orange juice and the grape juice, the calcium liquid, prepared by dissolving in vinegar the reprocessed calcium powder according to the present invention, was found not to significantly change the pH and total acidity of the juices. These results indicate that the calcium liquid can be used as a food additive.
EXPERIMENTAL EXAMPLE 7: Evaluation of the absorption rate of the high-content calcium liquid according to the present invention
The absorption rate of the high-content calcium liquid according to the present invention was investigated for six months with 12 healthy volunteers, who were women at the fifty
years of age and lived in the Daegu city, Kyungbuk, Korea.
The subjects were divided into a control group and two calcium-receiving groups I and II, each of which consisted of four women. In this test, the calcium liquid as a juice additive, prepared in Example 5, was used as a calcium supplement in a mixed form with an herbal extract.
2 g of Lycium Chinese, 5 g of eucommia bark, 0.2 g of anthlers, 4 g of achyranthes, 7 g of Angelicae gigantis, 7 g of the Cnidium plant, 10 g of cassia bark, 20 g of jujubes, 0.2 g of ginseng and 10 g of arrow roots were added to 1000 ml of distilled water. An extraction process was carried out at
120°C for 3 hrs. The herbal extract was filtered. Then, 89.97 ml of the herbal extract was mixed with 2.00 ml of an apple concentrate of 50° Brix, 10.00 ml of the calcium liquid, 5.00 ml of fructose, 0.03 ml of salt and 2.00 ml of honey, thus yielding a herbal calcium drink (calcium content: 237.3
' mg/pack) .
The calcium-receiving group I was received with two packs of the herbal calcium drink daily, while the calcium- receiving group II was received with three packs of ■ the calcium-enriched herbal calcium drink daily. The control group was received with two packs of an herbal solution containing the same ingredients as in the herbal calcium drink except for the calcium liquid, in order to exclude psychological factors and the influence of the herbal ingredients contained in the herbal calcium drink.
On the other hand, a dietary intake survey was carried out using a 24-hour recall method. In this survey, kinds and amounts of foods ingested for 24 hrs on the day before the
survey and ingredients of the foods were recorded. When the subjects did not exactly recall the ingested foods, they received helps with various dietary schedule models for one meal and photographs showing the models. The resulting records were analyzed using a nutritional evaluation program, CAN-PRO, which was developed by the Nutritional Information Center under the Korean Nutrition Institute.
Body compositions were measured by skilled personnel.
Height and body weight of the subjects were measured and used to calculate body mass index (BMI) . Body fat and WHR were calculated by using a body composition analyzer (Inbody 3.0,
Biospace Co. Korea) .
Bone mineral density was measured in the L2 to L4 of the lumber spine using a bone desitometer using a double energy radiation (Hogomic QDR-4500, USA) . Also, the bone mineral density was measured at the calcaneus using a bone densitometer using an ultrasonic wave (Quantative ultrasound bone imaging scanner UBIS 3000, France) .
In the biochemical assay, serum calcium levels were measured in serum samples collected from the subjects upon fasting using an automatic analyzer (Hitachi747, Japan) . A bone formation marker, osteocalcine, was detected by an immunoradiometic assay using a radioisotope (OSCA kit, Brahms Co., Germany), where the radioactivity was analyzed by a gamma counter. A bone absorption marker, deoxypyridinoline (D-pyr) , was detected in the urine of the subjects using a Pyrilinks-D kit (Metra Biosystmeics Inc., America), and each of the measured D-pyr levels was divided by the urine creatin level and expressed as "nmol/mmol Cr".
On the other hand, in all of the assays, mean and standard deviation (SD) values were calculated using a SPSS
(Statistical Package for the Social Science) program. Bone mineral density according to the ingestion of the calcium supplement and its clinical influences were analyzed by the
ANOVA procedure. Duncan' s test was carried out to determine whether variables have a significant difference.
As described above, the calcium liquid according to the present invention was evaluated for bioavailability in the form of the herbal calcium drink. The results are as follows.
As described above, the clinical subjects were first checked for average calcium intake and healthy states by investing their daily dietary intake and body composition. The 12 subjects were divided into three groups, and received with the herbal calcium drink or the herbal solution not containing calcium for six months.
The average age and body composition of the control group and the calcium-receiving groups I and II are given in Table 46, below. Members of each group were selected within the range with no difference between the groups in average age, height, body weight, BMI and body fat. The measured daily total calorie intake and calorie intake per nutrient are given in Table 47, below.
TABLE 46 Average age and body composite of the subjects per test group
TABLE 47 Daily total calorie intake and daily calorie intake per nutrient
The calcium-receiving group I showed the highest daily total calorie intake of about 1751 Kcal. Daily intake of carbohydrates, proteins and fats was found in similar levels among the groups. All of the subjects did not meet the recommended Korean daily calcium intake. In case of phosphor that plays an important role in the absorption of calcium, the phosphor intake was found to be higher than the calcium intake.
The excessive phosphor ingestion in comparison with the ingested amount of calcium can reduce the absorption rate of calcium. Based on these results, the twelve subjects were divided into the three groups, each of which consisted of four subjects.
The bone mineral density measured before and after the
clinical test for six months is given in Table 48, below. As shown in Table 48, osteopenia was observed in all of the subjects before the clinical test.
TABLE 48 Changes in bone mineral density of the clinical groups
If a normal person has a bone mineral density T-score value of 1, a T-score value of -1 indicates that a patient has osteopenia, while a T-score value of -2 indicates that a patient has osteoporosis. In this regard, all of the subjects were found to suffer from osteopenia. In particular, the calcium-receiving group II showed the lowest bone mineral density (BMD) T-score of -1.8. However, after the clinical period of six months, the calcium liquid-receiving groups I and II showed an increase in BMD or maintained BMD, whereas the control group not administered with the calcium liquid showed a decrease in BMD. BUA and SOS measurements were carried out at
the calcaneus, and the results are given in the above Table 48. Typically, the BUA and SOS values decrease as BMD decreases. In this clinical test, the calcium liquid-receiving groups I and II displayed a mild decrease in BUA and SOS in comparison with the control group. The biochemical assay results for the clinical subjects are given in Table 49. All of the subjects were found to have increased levels of serum calcium. However, the calcium liquid-receiving groups I and II showed higher increases in serum calcium than the control group. In addition, the level of the bone formation marker, osteocalcin typically increases in serum of patients suffering from osteoporosis. Serum osteocalcine levels were elevated in all of the clinical subjects. However, the calcium liquid- receiving groups I and II showed a higher increase in serum osteocalcine levels than the control group (see, Table 49) .
TABLE 49
Serum calcium, serum osteocalcin and urine deoxypyridinoline levels in the clinical groups
The level of the bone absorption marker deoxypyridinoline is known to increase in urine of patients suffering from osteoporosis. Urine deoxypyridinoline levels were reduced in all of the clinical subjects. In particular,
the calcium liquid-receiving groups I and II showed a higher decrease in urine deoxypyridinoline levels than the control group.
In this clinical test, the postmenopausal women at the fifty years of age were difficult to maintain body calcium levels during the clinical period. In contrast, in all of the subjects administered with the calcium-enriched herbal pouch drink containing the calcium liquid according to the present invention, BMD, calcium content, serum osteocalcin and the like were improved. These results indicate that the calcium liquid has high bioavailability and thus is highly functionable . Also, the control group not received the calcium liquid showed good results, indicating that the herbal solution positively affects bone formation.
Industrial Applicability
As described hereinbefore, the present invention provides a solvent capable of increasing solubility of calcium, a calcium powder with enhanced solubility, which is prepared using the solvent, and a calcium liquid prepared using the calcium powder. The calcium powder and the calcium liquid can be used as a food additive or as a beverage. Thus, this ■ invention is very useful in the food industry field.
Claims
1. A method of preparing a solvent for dissolution of calcium, comprising: mixing 97.14% (w/w) of apple vinegar with a total acidity of 6.6, 0.2% (w/w) of phosphoric acid, 0.15% (w/w) of lactic acid, 1.2% (w/w) of a tangle extract and 1.3% (w/w) of a malt extract.
2. A method of preparing a highly-soluble reprocessed calcium powder, comprising: dissolving calcium carbonate or aqua calcium in the solvent prepared according to the method of claim 1; and drying the resulting solution.
3. A method of preparing a highly-soluble reprocessed calcium powder, comprising: adding 17.50-20.00% (w/v) of calcium carbonate and 6.7-
7.8% (w/v) of dextrose to the solvent prepared according to the method of claim 1; dissolving the calcium carbonate and the dextrose in the solvent; homogenizing the resulting solution; and spray-drying a homogenized solution.
4. A method of preparing a highly-soluble reprocessed calcium liquid, comprising: dissolving the calcium powder prepared according to the method of claim 3 in a vinegar as a solvent.
5. The method as set forth in claim 4, wherein the calcium powder is used in an amount of 10% (w/v) based on the amount of the vinegar.
6. The method as set forth in claim 4, wherein the vinegar has an initial acidity of 6.5.
7. The method as set forth in claim 4, wherein the vinegar has a pH of 2.
8. The method- as set forth in claim 4, further comprising mixing activated carbon with the vinegar after the calcium powder is dissolved in the vinegar.
9. The method as set forth in claim 4, wherein the solvent is prepared by mixing 91.6298 wt% of a breed vinegar with a total acidity of over 6.5, 1.4000 wt% of glucose, 0.3500 wt% of phosphoric acid, 0.3000 wt of lactic acid, 0.1000 wt% of acetic acid, 0.0200 wt% of citric acid, 0.0001 wt% of an antifoamer and 0.0001 wt% of grape flavor.
10. The method as set forth in claim 8, wherein the activated carbon is used in an amount of 0.03% (w/v).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2003-0001973 | 2003-01-13 | ||
| KR20030001973 | 2003-01-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2004063095A2 true WO2004063095A2 (en) | 2004-07-29 |
| WO2004063095A3 WO2004063095A3 (en) | 2004-10-07 |
Family
ID=32709857
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/KR2004/000031 WO2004063095A2 (en) | 2003-01-13 | 2004-01-10 | Method for production of solvent for high solution of calcium, calcium powder with high solubility thereof and calcium liquid thereof |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR100547007B1 (en) |
| WO (1) | WO2004063095A2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011254809A (en) * | 2010-05-14 | 2011-12-22 | Sanei Gen Ffi Inc | Method for masking sour taste |
| CN109561726A (en) * | 2016-04-28 | 2019-04-02 | 泉标食品有限公司 | Fermentation apple products containing a large amount of calcium ions |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20060083282A (en) * | 2005-01-14 | 2006-07-20 | 최희욱 | Calcium ion drink that intake uses posible hi-condensed calcium aqueous solution manufacture method and this |
| CN111549239B (en) * | 2019-02-08 | 2022-04-22 | 北京中金瑞丰环保科技有限公司 | Resourceful treatment method of magnesium-containing raw material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4426308A (en) * | 1981-12-21 | 1984-01-17 | Gancy Alan B | Process of making calcium acetate deicing agents |
| US5215769A (en) * | 1990-10-31 | 1993-06-01 | The Procter & Gamble Company | Calcium fortified dressing salad product |
| US5811147A (en) * | 1994-06-16 | 1998-09-22 | Yamada; Youjiro | Mineral preservative |
| US20020114868A1 (en) * | 1999-03-09 | 2002-08-22 | Lederman Steven N. | Highly soluble and stable nutritional compositions containing calcium and magnesium |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0679542B2 (en) * | 1987-01-24 | 1994-10-12 | 泰 高橋 | Vinegar and / or acetic acid-containing feed |
-
2004
- 2004-01-10 WO PCT/KR2004/000031 patent/WO2004063095A2/en active Application Filing
- 2004-01-12 KR KR1020040001956A patent/KR100547007B1/en not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4426308A (en) * | 1981-12-21 | 1984-01-17 | Gancy Alan B | Process of making calcium acetate deicing agents |
| US5215769A (en) * | 1990-10-31 | 1993-06-01 | The Procter & Gamble Company | Calcium fortified dressing salad product |
| US5811147A (en) * | 1994-06-16 | 1998-09-22 | Yamada; Youjiro | Mineral preservative |
| US20020114868A1 (en) * | 1999-03-09 | 2002-08-22 | Lederman Steven N. | Highly soluble and stable nutritional compositions containing calcium and magnesium |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011254809A (en) * | 2010-05-14 | 2011-12-22 | Sanei Gen Ffi Inc | Method for masking sour taste |
| CN109561726A (en) * | 2016-04-28 | 2019-04-02 | 泉标食品有限公司 | Fermentation apple products containing a large amount of calcium ions |
| EP3449737A4 (en) * | 2016-04-28 | 2020-01-08 | Sempio Foods Company | Fermented apple product containing great quantity of calcium ion |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20040064647A (en) | 2004-07-19 |
| KR100547007B1 (en) | 2006-01-31 |
| WO2004063095A3 (en) | 2004-10-07 |
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