![]() Sodium ion-free effervescent tablet or effervescent powder with high calcium ion content (CaCO3).
专利摘要:
The process is used to prepare sodium-ion-free calcium carbonate effervescent tablets. The active substances, at least calcium carbonate moistened with a little alcohol and water are mixed as powder in a vacuum vessel with constant pumping in a partial vacuum with little lactobionic acid. As a result, calcium salt (CaCO 3) of calcium in the surface layer of the powder particles reacts with the lactobionic acid, brewing and releases little CO 2. As a result, the pressure in the vacuum vessel increases, and after the end of the showering reaction, the internal pressure in the vacuum vessel decreases by the constant pumping back to the initial value. The powder dries out. After removal from the vacuum pot citric acid is added as an effervescent and it is then pressed into tablets. The sodium-ion-free calcium carbonate effervescent tablet thus produced therefore contains at least calcium carbonate and citric acid as effervescent agents, wherein the compressed particles are brewed in their surface layer by means of lactobionic acid. 公开号:CH710361A2 申请号:CH01758/14 申请日:2014-11-12 公开日:2016-05-13 发明作者:Strobel Hanspeter 申请人:Laboratoires Biofar Sàrl; IPC主号:
专利说明:
This invention relates to a method for producing sodium ion-free effervescent tablets as calcium suppliers, said effervescent tablets should be rapidly and completely soluble in water. Food products made for general consumption are often altered by nutritional supplements or other types of additives to improve their nutritional properties. Nutrient fortification of food products may include additives that are conducive to the overall health of the human body. Examples of nutrient enhancement include the addition of vitamins, minerals and similar materials. These additives are either absolutely necessary for human metabolism or they promote the supply of substances that are not available in sufficient quantities in a normal diet. In the recent past, calcium fortification of foods and beverages has received significant attention. Calcium fortification and increased calcium intake have been reported to be particularly useful in preventing or mitigating the effects of osteoporosis. Increased dietary calcium intake has been shown to be effective in minimizing bone loss in adults and the elderly. In addition, increased calcium intake in younger years can create reserves that allow for greater tolerance of a negative calcium balance in later years. Increased calcium consumption, regardless of age, is expected to moderate or delay the effects of osteoporosis. Therefore, individuals of all ages could benefit from increased calcium consumption. Unfortunately, many of those most in need of calcium, including children, women and the elderly, do not consume the recommended daily amounts of calcium. According to surveys of the United States Department of Agriculture consume e.g. nine to ten women in the US do not have the recommended calcium levels. Older people often struggle to increase their calcium intake because of decreasing appetite and metabolism. In addition to bone health, recent research points to the importance of calcium in improving colon health, weight control and other health criteria. The current daily recommended value for calcium intake in the art is 1000 mg per day. These calcium supplements have been used in a wide variety of food products. U.S. Patent 4,784,871 (November 15, 1988) saw e.g. a calcium fortified yoghurt. According to the patent, any acid-soluble calcium compound could be used. U.S. Patent 5,449,523 (September 12, 1995) and U.S. Patent No. 5,820,903 (October 13, 1998) also provided calcium fortified yogurts. U.S. Patent 5,478,587 (December 27, 1995) noted calcium fortified desserts. U.S. Patent 5,834,045 (November 10, 1998) noted calcium fortified acidic beverages. This patent reported that the use of a calcium source containing calcium hydroxide and calcium glycerophosphate with an acidifying agent gives a beverage product with a marked improvement in shelf life. U.S. Patent 5,855,936 (January 5, 1999) described a mixture of calcium salts in equilibrium with soluble and insoluble salts stabilized with a source of glucuronic acid. This composition can enhance milk drinks and other milk-based products without coagulation and sedimentation and with improved palatability. The calcium salts must be stabilized with the glucuronic acid source. Other calcium sources could optionally be included. Other calcium fortified beverages are described, for example, in U.S. Patent 4,642,238 (February 10, 1987, Dietetic and Nutritionally Balanced Drinks); U.S. Patent 4,701,329 (October 20, 1987, Milk); U.S. Patent 4,737,375 (April 12, 1988, carbonated and non-carbonated beverages with solubilized calcium and specific amounts. Conventionally, there are also effervescent tablets for supplying calcium as a supplement for the needs of the human and animal body. These calcium effervescent tablets have been known for many decades, but they always use sodium ion (HST) to ensure solubility in water. Sodium has the negative effect of increasing blood pressure because it retains water in the blood, which can be critical in older people with slower digestion and increases the risk of stroke or thrombosis. The effervescent tablets should therefore contain no sodium ion or sodium bicarbonate. These calcium ion effervescent tablets are administered in calcium deficiency and vitamin D deficiency or also used to combat and dissolve urinary stones, such as kidney stones, bladder stones or ureteral stones, that is, deposits of urinary salts. The citrates contained in Blemaren alkalize the urine, which means they increase the pH of the urine. As a result, stones can be dissolved or prevented from growing. A typical composition of such an effervescent tablet contains, for example, with respect to calcium and sodium ion:<tb> calcium carbonate <SEP> 3000 <SEP> mg (equivalent to 1200mg calcium)<Tb> calcium ion <September> 1201.29 <September> mg<Tb> sodium <September> 320 <September> mg<tb> Sodium Ion (HST) <SEP> 101 <SEP> mg<Tb> citric <September> 5500 <September> mg<Tb> Colecaliciferol <September> 0:02 <September> mg<tb> Colcacifero <SEP> 800 I.E. <SEP> (International Units)<tb> and other ingredients, with a total weight of 9 241 mg. The object of this invention is to provide a method as a calcium-ion effervescent tablet can be prepared which manages without soda and is still dissolved quickly and completely in water by showering, as well as specify the necessary ingredients of the effervescent tablet. The object is achieved by a method for producing sodium-ion-free effervescent tablets, in which the active substances, at least calcium carbonate moistened with little alcohol and water are mixed as a powder in a vacuum pot with constant pumping in a partial vacuum with little lactobionic acid whereby the calcium salt of calcium in the surface layer of the powder particles reacts with the lactobionic acid and brews and releases little CO2, whereby the pressure in the vacuum pot rises and, after the showering reaction has ended, the pressure in the partial vacuum drops again to the initial value Dried out powder and after removal from the vacuum pot it is added citric acid as an effervescent agent, it is compressed into tablets. Next, the object is achieved by sodium ion-free effervescent tablets prepared by this method, containing at least calcium carbonate and citric acid as effervescent, wherein the compressed particles are brewed by Lactobionsäure in their surface layer. As an example of a composition of an effervescent tablet with calcium carbonate as the main constituent, the following composition is used:<tb> calcium carbonate <SEP> 3000 <SEP> mg (equivalent to 1200 mg calcium)<Tb> potassium <September> 380 <September> mg<Tb> lactobionic <September> 180 <September> mg<tb> citric acid anhydrous <SEP> 5000 <SEP> mg<Tb> Colecaliciferol <September> 0:02 <September> mg<Tb> Colcacifero <September> 800 <September> I.E. (International Units) Calcium carbonate is actually nothing else than marble, which is present in very fine powder. And this powder does not dissolve in the water practically, namely only 0.014 grams of calcium carbonate can be dissolved in one liter of water. With CO2 bubbles in the water, however, up to 16.6 grams of calcium carbonate can be dissolved in one liter of water. It is therefore important to first generate the gas CO2 in the water. And for this purpose, for example, potassium hydrogen carbonate can be used excellently, because in small amounts potassium hydrogen carbonate is considered a food additive and can therefore be safely used for this purpose. 380 mg of potassium bicarbonate are sufficient for 3000 mg of calcium carbonate, which is then used to brew and thus produce CO 2 with lactobionic acid. The resulting CO2 on the one hand then causes a significant improvement in the water solubility of calcium carbonate, namely up to 16.6 grams per liter of water. In principle, potassium bicarbonate is used in conjunction with the lactobionic acid as a starter for the solubility process for the calcium carbonate. The Anbrausung the powder particles of the moistened active substances by means of lactobionic causes an irregular decomposition of the surface layer in which there govern individual calcium salt particles from the calcium with the lactobionic acid and CO2 release, which makes the surface layer of the particles porous and rough. Then dry the previously moistened with alcohol and water powder in a partial vacuum. If necessary, this process can be repeated to produce an intimate nuisance. The thus prepared powder is mixed with citric acid as an effervescent and then pressed into tablets. The effervescent tablets thus produced are used for mineral reinforcement of food and beverage products. They form a stable, pure-tasting calcium source suitable for calcium fortification of very diverse food and beverage products. Lactobionic acid is generally a white crystalline powder. Lactobionic acid can be obtained commercially (e.g., Lonza Inc., Fairlawn, N.J., Sigma, St. Louis, MO) or prepared by chemical or enzymatic oxidation of lactose or a lactose-containing substrate. The lactobionic acid can be prepared by chemical saccharide oxidation or bioconversion processes (e.g., catalytic action of a carbohydrate oxidase enzyme) using lactose or a lactose-containing substrate (e.g., whey or whey permeate) as a starting material. In principle, lactobionic acid is a by-product of the dairy industry. Suitable carbohydrate oxidase enzymes are e.g. Lactose oxidase, glucose oxidase, hexose oxidase and the like and mixtures thereof. In general, lactose oxidase is preferred. A particularly suitable enzyme for lactose oxidation was developed by Novozymes NS and is described in WO 99/31990. The inventive method allows the production of effervescent tablets or effervescent granules, which not only have excellent storage stability, but also in their quality are always consistent, since the reproducibility of the process is ensured by controlling a number of reaction parameters at any time. The process for the preparation of effervescent tablets or processable effervescent granules is carried out by heat treatment at 30 ° C to 100 ° C of acid and bicarbonate and / or carbonate as essential effervescent components. The pulverulent or granular mixture is treated in a closed system in a partial vacuum, wherein the acid is optionally mixed after a pretreatment at elevated temperature with the necessary amount of bicarbonate and / or carbonate and then this mixture of a vacuum treatment at a temperature of 30 ° C. to 100 ° C, preferably 40 ° C to 80 ° C, at which it is treated with a polar solvent such as water, alcohol, methanol, ethanol or mixtures thereof. For passivation of the surface layer of at least one of the reaction components or for converting the same into a state of high reaction inertia during the vacuum treatment, a metered amount of up to 7% by mass, based on the mass of the mixture, of lactobionic acid is added. As a result of the resulting reaction developing CO2 evolution can increase the pressure in the vacuum vessel, up to max. 1000 mbar (atmospheric pressure). From the pressure difference to the initial value of, for example, 10 mbar in a vacuum vessel, the volume and mass of the CO2 released can be determined. The heat treatment, in each case after the rapid vacuum drying of the mixture, can be repeated until the surface passivation indicated by significant slowing of the reaction or reduced evolution of gas is reached. The aggregates obtained are then comminuted to a desired particle size, optionally provided with the desired additives and then tableted by means of a tablet press to effervescent tablets. The temperature at which the process according to the invention is carried out is not critical and is best between 40 and 80 ° C. The negative pressure at which work is to be as low as possible. Thus, the initial partial vacuum may have a pressure of, for example, 10 mbar. The polar solvent is preferably water used in an amount of 0.2 to 2% by mass based on the weight of the mixture to be treated. In carrying out the inventive method, it has been shown that when using suitable concentrations of the reactants and suitable amounts of polar solvent, only a portion of the reactants has reacted and that soon after the expiration of 10-20 min. the reaction becomes much slower. Now, if the thus reacted and slowly further stirred mixture is dried suddenly, then this process can be repeated under suitable conditions, which it turns out in the repetition that said process is slowed down, because a large part of the surface of the acid already by Alkali or alkaline earth salts passivated and made inert. Now, if the same reaction is carried out a third time, then you can see that almost no reaction takes place, since the entire surface is already passivated and the individual reaction partners are buffered in themselves. Thus, an inert mixture has arisen which, even when in contact with small amounts of polar solvents, no longer reacts or reacts only very slowly. It is obvious that the mixtures produced in the dry state have a very high stability even at higher temperatures, so that access of humidity or long storage at higher temperatures can cause no further reactions. Since, in accordance with the invention, the released amount of CO 2 is determined, one can determine in the course of simple stoichiometric calculations how much bicarbonate is consumed or how much salt was formed with the lactobionic acid. It is now in the hand, through suitable parameters such as stirring speed, the amount of moisture used of e.g. Water and alcohol, the grain size of the lactobionic acid used to determine how much lactobionic acid has been converted at the surface thereof to the acid salt. If, for example, 40 kg of a reaction mixture are reacted in a sealed 100 l vessel, the free space between the mass and the contents of the vessel, depending on the bulk density of the mass, will be about 50 l. If the vessel has been evacuated before the reaction, then this 50 l free space will be virtually gas-free. If a quantity of moisture is allowed to flow into the mass with simultaneous stirring, then the corresponding carbon dioxide will fill the supernatant space of 50 liters. This filling of the room can be easily checked with a good gauge. So has the initial partial vacuum 10mbar and has increased by the reaction, the pressure in the vacuum vessel to, for example, atmospheric pressure, then that means that about 50 liters of carbon dioxide were developed. It can now be recalculated how much lactobionic acid is consumed in this case or how much lactobionic acid citrate was produced. The repeated repetition of the described vacuum treatment almost halts the reaction between the reactants, ie the lactobionic acid and the calcium salt of calcium. Even in the presence of polar solvents and despite the small amounts of reacted materials, it is hardly possible to detect a reaction, so that after the product has been finally dried, an extremely resistant but still reactive mass is obtained. Moreover, the results are strictly reproducible while maintaining the aforesaid parameters and ensure the recovery of a product of consistently consistent quality. As a theoretical explanation for the effect achieved by the inventive method can be said that the contact surfaces of the reactants form a buffer zone, which are formed by various alkali or alkaline earth metal salts of the corresponding acid. Of course, these buffer zones will be formed depending on the surface of the individual crystals and the reactivity. An example: In a 100 liter vacuum kettle, 29 kg of citric acid and 1 kg of lactobionic acid are taken and heated with stirring for 5 min at 60 ° C, after which the residual moisture is briefly evacuated to 20mbar to control. After releasing the vacuum, 10 kg of calcium carbonate are added, followed by further heating to 60 ° C with further stirring. The mixture consisting of lactobionic acid then has a bulk density of approximately 1250 kg / m3, so that the space remaining in the vacuum vessel is about 50 liters. Then it is evacuated to 10 mbar, shut off by the pump by means of a valve and introduced with stirring, a quantity of 210 ml of water. At the onset of reaction between the lactobionic acid and the bicarbonate to form a passivating surface layer on the acid crystals and evolution of CO2, the pressure in the vacuum vessel increases from 10 mbar to 1000 mbar, corresponding to a volume of CO2 liberated of 50 l or a molar volume of CO2 60 ° C of 27.1 liters corresponds to a mass of released CO2 of 81g. As a result, in this first vacuum treatment, part of the lactobionic acid reacted with the surface layer of the particles, that is, the calcium salt of calcium, releasing CO2. The reaction time is about 4 min. Now the treated material is dried and vacuum-treated, repeated under the same conditions and using 300 ml of water. The pressure in the vacuum vessel is then allowed to rise again to 1000 mbar, corresponding to a volume of 50 l or a mass of 81 g of CO2. Due to the achieved in the first treatment partial Anbrausung of the surface layer by the Lactobionsäure this time the reaction time is already much longer and is about 10 to 30 min. The treated material is again dried and subjected to a third vacuum treatment, wherein now a slight increase in pressure is measured because the Lactobionsäure is used up, so that substantially no CO2 evolution takes place. The surface of the acid crystals is largely roughened or passivated, which means that no further reaction takes place. The product is then dried and the resulting agglomerates can be comminuted to the desired particle size, with the desired additives such as flavorings, vitamins, sweeteners and the like added. For later effervescing, citric acid is added in a conventional manner. If desired, this effervescent granulate can be pressed into effervescent tablets in a known manner by means of taping presses. The product obtained in this way has an excellent shelf life over long periods even at tropical temperatures. The showering is accelerated by the described pretreatment by means of lactobionic acid and depth effective, because all powder particles are "brewed", that is, they offer a much larger surface for later reaction with the added citric acid, as soon as the effervescent tablet comes into contact with water. If such an effervescent tablet prepared in water at room temperature, so this penetrates quickly into the surface layer of the powder particles and leads to a showering effect, which progressively rapidly dissipates the whole effervescent tablet against the interior and dissolves completely in water. After less than 3 minutes the effervescent tablet is completely dissolved and the solution is even clear.
权利要求:
Claims (6) [1] 1. A process for preparing sodium-ion-free calcium carbonate effervescent tablets, in which the active substances, at least calcium carbonate moistened with a little alcohol and water are mixed as a powder in a vacuum vessel with constant pumping in a partial vacuum with little lactobionic acid, whereby the Calcium salt of calcium in the surface layer of the powder particles reacts with the Lactobionsäure, verbraust and little CO2freisetzt, whereby the pressure in the vacuum pot increases and after the end of the effervescent reaction by the constant pumping the pressure in a partial vacuum drops back to the initial value, while the powder dries out and After removal from the vacuum pot it is added citric acid as an effervescent and it is then pressed into tablets. [2] 2. A method for producing sodium-ion-free calcium carbonate effervescent tablets according to claim 1, characterized in that in addition potassium hydrogen carbonate is added, which roars with the Lactobionsäure and generates initial CO2, to start and improve the water solubility of the calcium carbonate. [3] 3. A process for preparing sodium-ion-free calcium carbonate effervescent tablets according to claim 1, characterized in that the addition of lactobionic acid in a partial vacuum several times, after which each time the pressure in the vacuum kettle rises more slowly until the surface layer of the calcium carbonate is completely passivated, and then the vacuum-dried powder is removed from the vacuum vessel and processed further. [4] 4. Sodium-ion-free calcium carbonate effervescent tablet, prepared by the method of any of claims 1 to 3, containing at least calcium carbonate and citric acid as effervescent, wherein the compressed particles are brewed by Lactobionsäure in their surface layer. [5] 5. Sodium-ion-free calcium carbonate effervescent tablet, prepared by the method of any of claims 1 to 3, containing at least calcium carbonate and potassium bicarbonate, and citric acid as effervescent, wherein the compressed particles are brewed by Lactobionsäure in their surface layer. [6] 6. Sodium-ion-free calcium carbonate effervescent tablet according to claim 4, comprising in addition to optional other substances at least calcium carbonate and calcium ion, and instead of sodium ion for solubilizing the calcium carbonate (CaCO3) powder surface only lactobionic acid, and Citric acid for effervescence when dissolving the effervescent tablet in water.
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同族专利:
公开号 | 公开日 WO2016075655A1|2016-05-19| CH710361B1|2018-12-28| US20170319471A1|2017-11-09| EP3217809A1|2017-09-20| US10485754B2|2019-11-26|
引用文献:
公开号 | 申请日 | 公开日 | 申请人 | 专利标题 EP0076340B1|1981-10-06|1984-08-15|Gerhard Dr. Gergely|Process for manufacturing effervescent granules which may be transformed, when required, into effervescent tablets| US4678661A|1983-09-28|1987-07-07|Gerhard Gergely|Effervescent composition and method of making same| JPH0562157B2|1983-09-28|1993-09-07|Gergely Gerhard| US4737375A|1985-12-26|1988-04-12|The Procter & Gamble Company|Beverages and beverage concentrates nutritionally supplemented with calcium| US4642238A|1986-02-03|1987-02-10|Ralston Purina Company|Process for the production of a mineral fortified protein composition| US4701329A|1986-02-10|1987-10-20|Borden, Inc.|Calcium-fortified milk| US4784871A|1986-04-29|1988-11-15|Marigold Foods, Inc.|Method for producing calcium fortified yogurt| HU217125B|1993-03-10|1999-11-29|Béres Rt.|Sugar- and sodium-free effervescens tablets and granules and process for producing them| US5449523A|1993-04-20|1995-09-12|The Ohio State University Research Foundation|Process for the manufacture of a calcium fortified yogurt with improved heat stability| US5478587A|1993-08-20|1995-12-26|Henry G. Kohlmann|Dessert composition| HU221814B1|1993-09-09|2003-01-28|Gergely, Gerhard|Effervescent granulated material and method for its preparation| US5500232A|1994-10-06|1996-03-19|Bristol-Myers Squibb Company|Calcium fortified beverages| US5855936A|1997-03-21|1999-01-05|Nestec S.A.|Food fortification| US5820903A|1997-06-30|1998-10-13|General Mills, Inc.|Calcium fortified yogurt and methods of preparation| DK1525798T3|1997-12-22|2012-03-05|Novozymes As|Carbohydrate oxidase and its use in baking| DE19814392A1|1998-03-31|1999-10-07|Hermes Fabrik Pharm Praeparate|Effervescent tablet containing calcium with an antihistamine as active ingredient| US20040170724A1|2003-02-28|2004-09-02|Kraft Foods Holdings, Inc.|Mineral complexes of lactobionic acid and method of using for mineral fortification of food products|CN111517519A|2020-05-08|2020-08-11|欣格瑞(山东)环境科技有限公司|Treatment method of citric acid cleaning waste liquid|
法律状态:
2017-03-15| PCAR| Change of the address of the representative|Free format text: NEW ADDRESS: DUFOURSTRASSE 116, 8008 ZUERICH (CH) | 2021-06-30| PL| Patent ceased|
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申请号 | 申请日 | 专利标题 CH01758/14A|CH710361B1|2014-11-12|2014-11-12|Sodium-ion-free effervescent tablet or effervescent powder with high calcium ion content .|CH01758/14A| CH710361B1|2014-11-12|2014-11-12|Sodium-ion-free effervescent tablet or effervescent powder with high calcium ion content .| PCT/IB2015/058756| WO2016075655A1|2014-11-12|2015-11-12|Method for the production of a sodium ion-free effervescent tablet, powder or granulate having a high x ion content, where x can be a variety of substances| US15/526,457| US10485754B2|2014-11-12|2015-11-12|Method for the production of a sodium ion-free effervescent tablet, powder or granulate having a high X ion content, where X can be a variety of substances| EP15820259.8A| EP3217809A1|2014-11-12|2015-11-12|Method for the production of a sodium ion-free effervescent tablet, powder or granulate having a high x ion content, where x can be a variety of substances| 相关专利
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