CN104388188B - Method for extracting triglyceride-type Antarctic krill oil and Antarctic krill phospholipid - Google Patents
Method for extracting triglyceride-type Antarctic krill oil and Antarctic krill phospholipid Download PDFInfo
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Abstract
一种提取甘油三酯型南极磷虾油和南极磷虾磷脂的方法,包括步骤:1、在萃取温度30~50℃,萃取压力15~30MPa条件下萃取南极磷虾粉20~180min,得甘油三酯型南极磷虾油;2、保持萃取条件,启动夹带剂泵,注入90~100%乙醇,夹带剂总注入量为物料重量的4~40%,继续萃取0.5~1h;3、经超临界二氧化碳法萃取后的南极磷虾粉,采用90~100%乙醇萃取南极磷虾磷脂。本发明可以提高南极磷虾油的提取率,分别获得高纯度的甘油三酯型南极磷虾油和南极磷虾磷脂,丰富磷虾油产品的种类。超临界二氧化碳法在浸提甘油三酯型虾油时,也将虾青素提取出来,避免了溶剂浸出法提取时脱溶剂过程中高温对其结构的破坏,最大限度的保持虾油的功能活性成分。A method for extracting triglyceride-type Antarctic krill oil and Antarctic krill phospholipids, comprising the steps of: 1. Extracting Antarctic krill powder for 20-180 minutes at an extraction temperature of 30-50° C. and an extraction pressure of 15-30 MPa to obtain glycerol Triester type Antarctic krill oil; 2. Keep the extraction conditions, start the entrainer pump, inject 90-100% ethanol, the total injection amount of the entrainer is 4-40% of the material weight, and continue the extraction for 0.5-1h; 3. The Antarctic krill powder extracted by the critical carbon dioxide method is extracted with 90-100% ethanol to extract the Antarctic krill phospholipid. The invention can improve the extraction rate of Antarctic krill oil, obtain high-purity triglyceride-type Antarctic krill oil and Antarctic krill phospholipid respectively, and enrich the types of krill oil products. Supercritical carbon dioxide method also extracts astaxanthin when leaching triglyceride-type shrimp oil, avoiding the damage to its structure during the desolventization process of solvent leaching method, and maintaining the functional activity of shrimp oil to the maximum extent Element.
Description
技术领域technical field
本发明涉及一种超临界二氧化碳法结合乙醇浸出法提取甘油三酯型南极磷虾油和南极磷虾磷脂的方法。The invention relates to a method for extracting triglyceride-type Antarctic krill oil and Antarctic krill phospholipid by combining supercritical carbon dioxide method and ethanol leaching method.
背景技术Background technique
近年来,由于海洋环境持续恶化和过度捕捞,传统渔业资源衰退严重,开发新的渔业资源已刻不容缓。南极磷虾(Euphausia superb)是地球上数量最大的单种生物资源。据估计,南极磷虾的总生物量约为3.79亿吨,每年成虾总产量约为3.42~5.36亿吨。南极磷虾已成为世界上最重要的潜在渔业资源,受到世界各主要渔业强国的关注。我国近年来也开始关注南极磷虾资源,并从2009年开始对南极磷虾进行探捕,2013年捕捞量已达20000吨。南极磷虾已经成为我国未来将重点开发利用的渔业资源。In recent years, due to the continuous deterioration of the marine environment and overfishing, the traditional fishery resources have declined seriously, and it is urgent to develop new fishery resources. Antarctic krill (Euphausia superb) is the largest single biological resource on Earth. It is estimated that the total biomass of Antarctic krill is about 379 million tons, and the total annual adult shrimp production is about 342-536 million tons. Antarctic krill has become the most important potential fishery resource in the world, and has attracted the attention of all major fishery powers in the world. In recent years, my country has also begun to pay attention to Antarctic krill resources, and began to explore Antarctic krill in 2009, and the catch in 2013 has reached 20,000 tons. Antarctic krill has become a fishery resource that my country will focus on developing and utilizing in the future.
南极磷虾油中磷脂含量较高,且磷脂中的脂肪酸部分以多不饱和脂肪酸为主,同时还含有高浓度的虾青素,这种特殊的组成赋予南极磷虾油抑制肝脂肪化、抗过敏、抗氧化、降血脂、降血糖及心脏保护等活性,具有极高的市场前景。目前,提取南极磷虾油的主要方法是有机溶剂浸出法。有机溶剂浸出法提取效率高,对极性、非极性油脂均可完全提取,易于工业化应用。然而,该方法工业化生产时也存在一些不利的方面,包括需要的厂区空间大,提取过程中可能需要高温操作易破坏热敏性生理活性物质,油中蛋白质、游离脂肪酸等杂质含量较高,溶剂残留不易克服可能影响油脂的安全性。The content of phospholipids in Antarctic krill oil is relatively high, and the fatty acid in phospholipids is mainly polyunsaturated fatty acids, and it also contains high concentration of astaxanthin. This special composition gives Antarctic krill oil inhibition of liver fatty Allergy, anti-oxidation, hypolipidemic, hypoglycemic and cardioprotective activities have extremely high market prospects. At present, the main method of extracting Antarctic krill oil is organic solvent leaching. The organic solvent leaching method has high extraction efficiency, can completely extract polar and non-polar oils, and is easy for industrial application. However, this method also has some disadvantages during industrial production, including the large space required for the plant, the high temperature operation that may be required during the extraction process, which can easily destroy heat-sensitive physiologically active substances, the high content of impurities such as protein and free fatty acids in the oil, and the difficulty of solvent residues. Overcome the safety that may affect the oil.
磷脂型多不饱和脂肪酸是南极磷虾油中的主要功效成分,因此生产磷脂含量高的南极磷虾油产品可以提升产品档次,增加产品的附加值。目前,磷脂的富集方法主要是丙酮纯化法、柱色谱分离法。丙酮法产品中丙酮易残留,影响使用安全性,而柱色谱分离法成本较高。Phospholipid-type polyunsaturated fatty acids are the main functional components in Antarctic krill oil, so the production of Antarctic krill oil products with high phospholipid content can improve the product grade and increase the added value of the product. At present, the enrichment methods of phospholipids are mainly acetone purification method and column chromatography separation method. Acetone is easy to remain in the product of acetone method, which affects the safety of use, while the cost of column chromatography is relatively high.
本发明利用超临界二氧化碳法与乙醇浸出法结合的方法提取南极磷虾甘油三酯和南极磷虾磷脂,不仅可以提高虾油的提取效率,还可以分别获得高纯度的甘油三酯型南极磷虾油和南极磷虾磷脂,丰富磷虾油产品的种类。此外,超临界二氧化碳法在浸提甘油三酯型虾油时,也将虾青素提取出来,避免了溶剂浸出法提取时脱溶剂过程中高温对其结构的破坏,可以最大限度的保持虾油的功能活性成分。The present invention uses the combination of supercritical carbon dioxide method and ethanol leaching method to extract Antarctic krill triglycerides and Antarctic krill phospholipids, which can not only improve the extraction efficiency of shrimp oil, but also obtain high-purity triglyceride-type Antarctic krill respectively oil and Antarctic krill phospholipids, enriching the types of krill oil products. In addition, the supercritical carbon dioxide method also extracts astaxanthin when extracting triglyceride-type shrimp oil, which avoids the damage to its structure during the desolventization process during solvent extraction, and can keep the shrimp oil to the maximum extent. functional active ingredients.
发明内容Contents of the invention
本发明的目的在于提供一种超临界二氧化碳法结合乙醇浸出法提取甘油三酯型南极磷虾油和南极磷虾磷脂的方法。首先对南极磷虾粉进行不加夹带剂的超临界二氧化碳法萃取得甘油三酯型南极磷虾油;然后保持萃取条件不变,启动夹带剂泵注入乙醇萃取以除去虾粉中残余的游离脂肪酸、甘油二酯及甘油一酯等脂质成分;最后以乙醇为溶剂采用浸出法对经超临界二氧化碳法萃取后的南极磷虾粉提取南极磷虾磷脂。The object of the present invention is to provide a method for extracting triglyceride-type Antarctic krill oil and Antarctic krill phospholipids by combining supercritical carbon dioxide method with ethanol leaching method. Firstly, the Antarctic krill powder is extracted by supercritical carbon dioxide method without entrainer to obtain triglyceride type Antarctic krill oil; then keep the extraction conditions unchanged, start the entrainer pump and inject ethanol extraction to remove the residual free fatty acid in the shrimp powder , diglyceride, monoglyceride and other lipid components; finally, the Antarctic krill phospholipids were extracted from the Antarctic krill powder extracted by supercritical carbon dioxide method by leaching with ethanol as solvent.
为了达到上述目的,本发明提供一种提取甘油三酯型南极磷虾油和南极磷虾磷脂的方法,包括如下步骤:In order to achieve the above object, the present invention provides a method for extracting triglyceride type Antarctic krill oil and Antarctic krill phospholipid, comprising the steps of:
S1、选用南极磷虾粉,利用超临界二氧化碳法,在萃取温度30~50℃,萃取压力15~30MPa条件下萃取南极磷虾粉20~180min,得甘油三酯型南极磷虾油。经棒状薄层色谱法检测,甘油三酯含量占总脂的85%以上。S1. Select Antarctic krill powder and use supercritical carbon dioxide method to extract Antarctic krill powder for 20-180 minutes at an extraction temperature of 30-50°C and an extraction pressure of 15-30 MPa to obtain triglyceride-type Antarctic krill oil. Detected by stick thin-layer chromatography, the triglyceride content accounts for more than 85% of the total fat.
S2、保持萃取条件不变,启动夹带剂泵,注入90~100%乙醇,所述夹带剂总注入量为物料重量的4~40%,继续萃取0.5~1h;除去虾粉中残余的游离脂肪酸、甘油二酯及甘油一酯等脂质成分。S2. Keep the extraction conditions unchanged, start the entrainer pump, inject 90-100% ethanol, the total injection amount of the entrainer is 4-40% of the material weight, and continue the extraction for 0.5-1h; remove the residual free fatty acid in the shrimp meal , diglycerides and monoglycerides and other lipid components.
S3、经步骤2萃取后的南极磷虾粉,用浸提溶剂90~100%乙醇提取磷脂,其中,所述虾粉重量:浸提溶剂重量为1:2.5~1:9,浸提温度20~60℃,浸提时间0.5~2.5h,提取液经低温真空干燥后得南极磷虾磷脂。经棒状薄层色谱法检测,磷脂含量占总脂的97%以上。S3. The Antarctic krill powder extracted in step 2 is extracted with 90% to 100% ethanol as an extraction solvent for phospholipids, wherein the weight of the shrimp powder: the weight of the extraction solvent is 1:2.5 to 1:9, and the extraction temperature is 20 ~60°C, leaching time 0.5~2.5h, the extract solution is vacuum-dried at low temperature to obtain Antarctic krill phospholipids. Detected by stick thin layer chromatography, the phospholipid content accounts for more than 97% of the total lipid.
其中,所述南极磷虾粉通过将南极磷虾进行冷冻干燥后,经粉碎、研磨获得。此外,步骤S2,游离脂肪酸、甘油二酯及甘油一酯等脂质成份极性强于甘油三酯,因此不加夹带剂时不易被超临界二氧化碳萃取,加入极性夹带剂后可被超临界二氧化碳萃取。而磷脂即使加入极性夹带剂也很不能被超临界二氧化碳萃取。Wherein, the Antarctic krill powder is obtained by crushing and grinding the Antarctic krill after freeze-drying. In addition, in step S2, lipid components such as free fatty acids, diglycerides, and monoglycerides are more polar than triglycerides, so they are not easily extracted by supercritical carbon dioxide when no entrainer is added, and can be extracted by supercritical carbon dioxide after adding a polar entrainer. Carbon dioxide extraction. Phospholipids cannot be extracted by supercritical carbon dioxide even if a polar entrainer is added.
本发明的技术创新在于:首先对南极磷虾粉进行超临界二氧化碳法萃取甘油三酯型南极磷虾油,然后保持萃取条件不变,启动夹带剂泵进行超临界二氧化碳法萃取除去虾粉中残余的游离脂肪酸、甘油二酯及甘油一酯等脂质成分,最后再对超临界二氧化碳法萃取后的南极磷虾粉,加入乙醇进行有机乙醇浸出法提取南极磷虾磷脂。该方法流程简单,质量稳定,且提取到的甘油三酯和磷脂的纯度较高。The technical innovation of the present invention is: firstly extract triglyceride-type Antarctic krill oil from Antarctic krill powder by supercritical carbon dioxide method, and then keep the extraction conditions unchanged, start the entrainer pump to carry out supercritical carbon dioxide extraction to remove residual shrimp powder Lipid components such as free fatty acids, diglycerides and monoglycerides, etc., and finally add ethanol to the Antarctic krill powder extracted by supercritical carbon dioxide method to extract Antarctic krill phospholipids by organic ethanol leaching. The process of the method is simple, the quality is stable, and the purity of the extracted triglyceride and phospholipid is high.
本发明利用超临界二氧化碳法与乙醇浸出法结合的方法提取甘油三酯和南极磷虾磷脂,不仅可以提高虾油的提取效率,还可以分别获得高纯度的甘油三酯型虾油和南极磷虾磷脂,丰富磷虾油产品的种类。此外,超临界二氧化碳法在浸提甘油三酯型虾油时,也将虾青素提取出来,避免了溶剂浸出法提取时脱溶剂过程中高温对其结构的破坏,可以最大限度的保持虾油的功能活性成分。In the present invention, triglyceride and Antarctic krill phospholipids are extracted by combining supercritical carbon dioxide method and ethanol leaching method, which can not only improve the extraction efficiency of shrimp oil, but also obtain high-purity triglyceride-type shrimp oil and Antarctic krill respectively Phospholipids, the type that enriches krill oil products. In addition, the supercritical carbon dioxide method also extracts astaxanthin when extracting triglyceride-type shrimp oil, which avoids the damage to its structure during the desolventization process during solvent extraction, and can keep the shrimp oil to the maximum extent. functional active ingredients.
具体实施方式detailed description
本发明提供一种超临界二氧化碳法结合乙醇浸出法提取甘油三酯型南极磷虾油和南极磷虾磷脂的方法,包括如下步骤:The invention provides a method for extracting triglyceride-type Antarctic krill oil and Antarctic krill phospholipids by combining supercritical carbon dioxide method with ethanol leaching method, comprising the following steps:
(1)将南极磷虾进行冷冻干燥后,再经粉碎、研磨,得到南极磷虾粉。(1) Antarctic krill is freeze-dried, then pulverized and ground to obtain Antarctic krill powder.
(2)南极磷虾粉,采用超临界萃取设备,在萃取温度30-50℃,萃取压力15-30MPa条件下萃取南极磷虾粉20-180min,获得甘油三酯型南极磷虾油。(2) Antarctic krill powder, using supercritical extraction equipment, extracting Antarctic krill powder for 20-180min at an extraction temperature of 30-50°C and an extraction pressure of 15-30MPa to obtain triglyceride-type Antarctic krill oil.
(3)保持萃取条件不变,启动夹带剂泵,注入90-100%乙醇,夹带剂总注入量为物料重量的4-40%,继续萃取0.5-1h,除去虾粉中残余的游离脂肪酸、甘油二酯及甘油一酯等脂质成分。(3) Keep the extraction conditions constant, start the entrainer pump, inject 90-100% ethanol, the total injection amount of the entrainer is 4-40% of the material weight, continue to extract for 0.5-1h, remove residual free fatty acid, Lipid components such as diglycerides and monoglycerides.
(4)超临界二氧化碳法萃取后的南极磷虾粉,用90-100%乙醇提取磷脂,虾粉重量:浸提溶剂重量为12.5-1:9,浸提温度20-60℃,浸提时间0.5-2.5h,提取液经低温真空干燥后得南极磷虾磷脂。(4) Antarctic krill powder extracted by supercritical carbon dioxide method, extract phospholipids with 90-100% ethanol, shrimp powder weight: extraction solvent weight is 12.5-1:9, extraction temperature is 20-60°C, extraction time After 0.5-2.5h, the extract was dried in vacuum at low temperature to obtain Antarctic krill phospholipid.
本发明制备的南极磷虾油主要成分及其含量:在步骤2所得南极磷虾油中甘油三酯的相对回收率在95%以上,甘油三酯含量占总脂的85%以上,在步骤4所得南极磷虾磷脂中磷脂的相对回收率在80%以上,磷脂占总脂的97%以上。其中,相对回收率是指提取到的成分占提取原料中该成分总量的百分比。The main components and contents of the Antarctic krill oil prepared by the present invention: the relative recovery rate of triglyceride in the Antarctic krill oil obtained in step 2 is more than 95%, and the triglyceride content accounts for more than 85% of the total fat, and in step 4 The relative recovery rate of the phospholipids in the obtained Antarctic krill phospholipids is over 80%, and the phospholipids account for over 97% of the total lipids. Wherein, the relative recovery rate refers to the percentage of the extracted component to the total amount of the component in the extracted raw material.
实施例1Example 1
(1)南极磷虾粉,采用超临界萃取设备,在萃取温度35℃,萃取压力20MPa,分离温度55℃,分离压力9MPa条件下萃取90min,得到甘油三酯型南极磷虾油,甘油三酯的相对回收率为98.30%,甘油三酯含量占总脂的86.64%。(1) Antarctic krill powder, using supercritical extraction equipment, extracted for 90 minutes at an extraction temperature of 35°C, an extraction pressure of 20MPa, a separation temperature of 55°C, and a separation pressure of 9MPa to obtain triglyceride-type Antarctic krill oil, triglyceride The relative recovery rate was 98.30%, and the triglyceride content accounted for 86.64% of the total fat.
(2)保持萃取条件不变,启动夹带剂泵,注入95%乙醇,夹带剂总注入量为物料重量的4%,继续萃取60min,除去非磷脂成分。(2) Keep the extraction conditions unchanged, start the entrainer pump, inject 95% ethanol, the total injection amount of the entrainer is 4% of the material weight, and continue the extraction for 60 minutes to remove non-phospholipid components.
(3)超临界二氧化碳法萃取后的南极磷虾粉,用95%乙醇提取高纯度磷脂,虾粉重量:浸提溶剂重量为1:2.5,浸提温度50℃,浸提时间1h,提取液经低温真空干燥后得南极磷虾磷脂,磷脂的相对回收率为88.19%,磷脂含量占总脂的98.35%。(3) Antarctic krill powder extracted by supercritical carbon dioxide method, extract high-purity phospholipids with 95% ethanol, shrimp powder weight: extraction solvent weight is 1:2.5, extraction temperature is 50°C, extraction time is 1h, and the extraction solution Antarctic krill phospholipids were obtained after low-temperature vacuum drying. The relative recovery rate of phospholipids was 88.19%, and the phospholipid content accounted for 98.35% of the total lipids.
实施例2Example 2
(1)南极磷虾粉,采用超临界萃取设备,在萃取温度35℃,萃取压力30MPa,分离温度55℃,分离压力9MPa条件下萃取90min,得到甘油三酯型南极磷虾油,甘油三酯的相对回收率为98.28%,甘油三酯含量占总脂的88.18%。(1) Antarctic krill powder, using supercritical extraction equipment, extracted for 90 minutes at an extraction temperature of 35°C, an extraction pressure of 30MPa, a separation temperature of 55°C, and a separation pressure of 9MPa to obtain triglyceride-type Antarctic krill oil, triglyceride The relative recovery rate was 98.28%, and the triglyceride content accounted for 88.18% of the total fat.
(2)保持萃取条件不变,启动夹带剂泵,注入98%乙醇,夹带剂总注入量为物料重量的8%,继续萃取60min,除去非磷脂成分。(2) Keep the extraction conditions unchanged, start the entrainer pump, inject 98% ethanol, the total injection amount of the entrainer is 8% of the material weight, and continue the extraction for 60min to remove non-phospholipid components.
(3)超临界二氧化碳法萃取后的南极磷虾粉,用98%乙醇提取高纯度磷脂,虾粉重量:浸提溶剂重量为1:5.6,浸提温度50℃,浸提时间1.5h,提取液经低温真空干燥后得南极磷虾磷脂,磷脂的相对回收率为93.74%,磷脂含量占总脂的98.46%。(3) Antarctic krill powder extracted by supercritical carbon dioxide method, extract high-purity phospholipids with 98% ethanol, shrimp powder weight: extraction solvent weight is 1:5.6, extraction temperature is 50°C, extraction time is 1.5h, extraction The Antarctic krill phospholipid was obtained after the liquid was dried in vacuum at low temperature. The relative recovery rate of the phospholipid was 93.74%, and the phospholipid content accounted for 98.46% of the total lipid.
实施例3Example 3
(1)南极磷虾粉,采用超临界萃取设备,在萃取温度40℃,萃取压力25MPa,分离温度55℃,分离压力9MPa条件下萃取90min,得到甘油三酯型南极磷虾油,甘油三酯的相对回收率为98.31%,甘油三酯含量占总脂的87.63%。(1) Antarctic krill powder, using supercritical extraction equipment, extracted for 90 minutes at an extraction temperature of 40°C, an extraction pressure of 25MPa, a separation temperature of 55°C, and a separation pressure of 9MPa to obtain triglyceride-type Antarctic krill oil, triglyceride The relative recovery rate was 98.31%, and the triglyceride content accounted for 87.63% of the total fat.
(2)保持萃取条件不变,启动夹带剂泵,注入96%乙醇,夹带剂总注入量为物料重量的24%,继续萃取60min,除去非磷脂成分。(2) Keep the extraction conditions unchanged, start the entrainer pump, inject 96% ethanol, the total injection amount of the entrainer is 24% of the material weight, and continue the extraction for 60 minutes to remove non-phospholipid components.
(3)超临界二氧化碳法萃取后的南极磷虾粉,用96%乙醇提取高纯度磷脂,虾粉重量:浸提溶剂重量为1:7.2,浸提温度40℃,浸提时间1h,提取液经低温真空干燥后得南极磷虾磷脂,磷脂的相对回收率为90.07%,磷脂含量占总脂的97.41%。(3) Antarctic krill powder extracted by supercritical carbon dioxide method, extract high-purity phospholipids with 96% ethanol, shrimp powder weight: extraction solvent weight is 1:7.2, extraction temperature is 40°C, extraction time is 1h, extraction solution Antarctic krill phospholipids were obtained after low-temperature vacuum drying. The relative recovery rate of phospholipids was 90.07%, and the phospholipid content accounted for 97.41% of the total lipids.
实施例4Example 4
(1)南极磷虾粉,采用超临界萃取设备,在萃取温度45℃,萃取压力30MPa分离温度55℃,分离压力8-10MPa条件下萃取90min,得到甘油三酯型南极磷虾油,甘油三酯的相对回收率为98.29%,甘油三酯含量占总脂的87.58%。(1) Antarctic krill powder, using supercritical extraction equipment, extracting for 90 minutes at an extraction temperature of 45°C, an extraction pressure of 30MPa, a separation temperature of 55°C, and a separation pressure of 8-10MPa, to obtain triglyceride-type Antarctic krill oil, triglyceride The relative recovery rate of ester was 98.29%, and the content of triglyceride accounted for 87.58% of the total lipid.
(2)保持萃取条件不变,启动夹带剂泵,注入96%乙醇,夹带剂总注入量为物料重量的32%,继续萃取60min,除去非磷脂成分。(2) Keep the extraction conditions unchanged, start the entrainer pump, inject 96% ethanol, the total injection amount of the entrainer is 32% of the material weight, and continue the extraction for 60 minutes to remove non-phospholipid components.
(3)超临界二氧化碳法萃取后的南极磷虾粉,用96%乙醇提取高纯度磷脂,虾粉重量:浸提溶剂重量为1:8.8,浸提温度40℃,浸提时间1.5h,提取液经低温真空干燥后得南极磷虾磷脂,磷脂的相对回收率为90.79%,磷脂含量占总脂的98.41%。(3) Antarctic krill powder extracted by supercritical carbon dioxide method, extract high-purity phospholipids with 96% ethanol, shrimp powder weight: extraction solvent weight is 1:8.8, extraction temperature is 40°C, extraction time is 1.5h, extraction Antarctic krill phospholipids were obtained after the solution was dried in vacuum at low temperature. The relative recovery rate of phospholipids was 90.79%, and the content of phospholipids accounted for 98.41% of the total lipids.
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明披露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。The above is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Anyone familiar with the technical field within the technical scope disclosed in the present invention, according to the technical solution of the present invention Any equivalent replacement or change of the inventive concepts thereof shall fall within the protection scope of the present invention.
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