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CN104431364B - Application of the natural organic acids root laminine chelate in feed - Google Patents

Application of the natural organic acids root laminine chelate in feed Download PDF

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CN104431364B
CN104431364B CN201410753008.5A CN201410753008A CN104431364B CN 104431364 B CN104431364 B CN 104431364B CN 201410753008 A CN201410753008 A CN 201410753008A CN 104431364 B CN104431364 B CN 104431364B
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chelate
organic acid
feed
natural organic
laminine
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CN104431364A (en
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李群
邵培源
李子超
谷正
赵昔慧
吕洲
李晓雯
王越
王艳玮
刘倩倩
朱善富
马苗
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Qingdao University
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Abstract

本发明公开了一种有机酸根褐藻氨酸螯合物作为抗生营养素在饲料中的应用,天然有机酸根褐藻氨酸螯合物一种或两种以上单独使用,将其作为抗生营养素应用在抗生营养饲料制造领域。天然有机酸根褐藻氨酸螯合物为复合机理,一方面天然有机酸根褐藻氨酸螯合物携带阳离子基团,可静电吸附细胞膜带负电荷的细菌等微生物抑制微生物细胞的呼吸机能而导致“接触死亡”;金属离子可与细胞内活性基团形成络合物或者螯合物,而使微生物不能繁殖甚至死亡,天然有机酸根褐藻氨酸与现有技术中的卤素负离子等相比,有更好的生物相容性,可生物降解,无毒副作用。因此,天然有机酸根褐藻氨酸螯合物具有良好的广谱抗微生物能力和营养供给能力。

The invention discloses the application of an organic acid root fucoidic acid chelate as an antibiotic nutrient in feed. One or two or more natural organic acid root fucoidic acid chelates are used alone and used as an antibiotic nutrient in an antibiotic nutrient. Feed manufacturing field. The natural organic acid radical fucoidin chelate is a composite mechanism. On the one hand, the natural organic acid radical fucoidin chelate carries a cationic group, which can electrostatically adsorb microorganisms such as negatively charged bacteria on the cell membrane and inhibit the respiratory function of microbial cells, resulting in "contact death”; metal ions can form complexes or chelates with active groups in cells, so that microorganisms cannot reproduce or even die. Biocompatibility, biodegradability, no toxic side effects. Therefore, the natural organic acid radical fucoidan chelate has good broad-spectrum antimicrobial ability and nutrient supply ability.

Description

天然有机酸根褐藻氨酸螯合物在饲料中的应用Application of natural organic acid radical fucoidin chelate in feed

技术领域technical field

本发明主要涉及一种将天然有机酸根褐藻氨酸螯合物用作抗生营养素,主要用作抗生营养饲料制造领域。The invention mainly relates to the field of using the natural organic acid radical fucoidic acid chelate as an antibiotic nutrient, mainly used in the manufacture of an antibiotic nutrient feed.

背景技术Background technique

褐藻氨酸是海藻中特有的一种具有降压生物活性的非蛋白质氨基酸,可以降低胆固醇,降低血脂,抗血小板凝聚,防止血管粥样硬化,有效地预防高血压和脑溢血的发生,安全高效,无毒副作用。金属离子在生物体内具有维持电解质平衡,构成蛋白质分子活性中心、抗微生物侵害等多种生物活性,天然有机酸根褐藻氨酸金属螯合物则兼具天然有机酸根褐藻氨酸和金属的双重生物活性,是未见报道的亟待开发的新型药物和功能添加剂。1964年日本竹本常松发现天然有机酸根褐藻(即海带)中存在一种具有降压活性的氨基酸,确认结构后命名为褐藻氨酸(Laminine),但因海带中褐藻氨酸的含量很低,所以目前不仅没有商品化,对其研究也仅限于生物活性方面;此后研究进展缓慢,直到1995年,孙世锡等人[降血压药物-天然有机酸根褐藻氨酸合成方法的研究[J].山东医药工业,1995,14(2):7-8]提出了褐藻氨酸的化学合成方法;专利CN200410024504.3公开了一种原料药-N-三甲基赖氨酸的清洁化生产与应用方法;在前者的基础之上,专利CN200610069978.9公开了一种高纯度褐藻氨酸的清洁化生产方法,使褐藻氨酸的研究和商业价值得到进一步提升。Fucoidic acid is a non-protein amino acid unique in seaweed with antihypertensive biological activity. It can lower cholesterol, lower blood lipids, resist platelet aggregation, prevent atherosclerosis, and effectively prevent hypertension and cerebral hemorrhage. It is safe and efficient. No toxic side effects. Metal ions have various biological activities in the body, such as maintaining electrolyte balance, constituting the active center of protein molecules, and resisting microbial invasion. The metal chelate of natural organic acid fucoidin has dual biological activities of natural organic acid fucoidin and metal. , is a novel drug and functional additive that has not been reported and urgently needs to be developed. In 1964, Takemoto Changmatsu found an amino acid with antihypertensive activity in natural organic acid root brown algae (kelp), and named it Laminine after confirming the structure. However, because the content of kelp is very low, so Not only is it not commercialized at present, but the research on it is limited to the aspect of biological activity; since then, the research has progressed slowly until 1995, Sun Shixi et al. ,1995,14(2):7-8] proposed a chemical synthesis method of alginic acid; patent CN200410024504.3 disclosed a clean production and application method of a raw material drug-N-trimethyllysine; On the basis of the former, patent CN200610069978.9 discloses a clean production method of high-purity alginic acid, which further improves the research and commercial value of alginic acid.

天然有机酸根褐藻氨酸金属螯合物虽然已有研究,属于抗癌活性领域,但是用作抗生营养素饲料的应用到目前未见报道。Although the metal chelate of natural organic acid radical alginate has been studied and belongs to the field of anticancer activity, the application of it as an antibiotic nutrient feed has not been reported so far.

发明内容Contents of the invention

本发明公开了一种天然有机酸根褐藻氨酸螯合物作为抗生营养素在饲料中的应用,其主要用作抗生、防病、补充营养等领域,本发明天然有机酸根褐藻氨酸螯合物具有良好的广谱抗微生物能力和营养供给能力。The invention discloses the application of a natural organic acid radical fucoidic acid chelate as an antibiotic nutrient in feed, which is mainly used in the fields of antibiotics, disease prevention, and nutritional supplementation. The natural organic acid radical fucoidic acid chelate of the present invention has Good broad-spectrum antimicrobial ability and nutrient supply ability.

其技术解决方案是:Its technical solutions are:

有机酸根褐藻氨酸螯合物作为抗生营养素的应用,所述有机酸根褐藻氨酸螯合物的分子式如(1-1):The application of the organic acid radical fucoidic acid chelate as an antibiotic nutrient, the molecular formula of the organic acid radical fuconic acid chelate is as (1-1):

其中,Y代表有机酸根褐藻氨酸螯合物阳离子形成晶体时的阴离子,所述阴离子包括柠檬酸根、酒石酸根、马来酸根、月桂酸根、棕榈酸根、乳酸根、抗坏血酸根或氨基酸根;M代表钙离子、铁离子、钴离子、锌离子、铜离子或混合轻稀土离子;所述应用为抗生营养饲料制造领域,所述有机酸根褐藻氨酸螯合物在抗生营养饲料中所占百分重量比均为1-10%。Wherein, Y represents the anion when the organic acid radical fucoidic acid chelate cation forms a crystal, and the anion includes citrate, tartrate, maleate, laurate, palmitate, lactate, ascorbate or amino acid radical; M represents Calcium ions, iron ions, cobalt ions, zinc ions, copper ions or mixed light rare earth ions; the application is in the field of antibiotic nutritional feed manufacturing, and the percentage weight of the organic acid radical fucoidic acid chelate in the antibiotic nutritional feed The ratio is 1-10%.

作为本发明的一个优选方案,上述有机酸根褐藻螯合物作为饲料添加剂时,每千克饲料转化蛋白率百分率为23.7%-27.4%。As a preferred solution of the present invention, when the above-mentioned organic acid radical brown algae chelate is used as a feed additive, the conversion protein rate per kilogram of feed is 23.7%-27.4%.

作为本发明的另一个优选方案,上述Y为氨基酸根,M为锌离子;以猪饲料为例,饲料储层保质期为10个月,每Kg饲料转化蛋白率百分率为27.9%。As another preferred solution of the present invention, above-mentioned Y is an amino acid root, and M is a zinc ion; taking pig feed as an example, the shelf life of the feed reservoir is 10 months, and the conversion protein rate per Kg feed is 27.9%.

本发明有机酸根褐藻氨酸螯合物的反应机理如下:The reaction mechanism of the organic acid radical fucoidin chelate of the present invention is as follows:

从抗微生物机理来看,天然有机酸根褐藻氨酸螯合物为复合机理,一方面天然有机酸根褐藻氨酸螯合物携带阳离子基团,可静电吸附细胞膜带负电荷的细菌等微生物抑制微生物细胞的呼吸机能而导致“接触死亡”;也能扩散至细胞膜内,抑制微生物细胞脱氢酶、氧化酶作用,使其失活;有机螯合状态的金属离子更易靠近细胞,可与微生物细胞内活性基团形成键合关系,而使微生物不能繁殖甚至死亡,两种作用可能存在在协同效应。同时,天然有机酸根维持弱碱性环境,褐藻酸有保湿性能,所选金属离子为生命元素,三者协效,可使饲料具有抗生、防病、补充营养作用,有更好的经济效益。From the perspective of antimicrobial mechanism, natural organic acid radical fucoidic acid chelate is a composite mechanism. On the one hand, natural organic acid radical fucoidic acid chelate carries cationic groups, which can electrostatically adsorb microorganisms such as negatively charged bacteria on the cell membrane to inhibit microbial cells It can also diffuse into the cell membrane, inhibit the action of microbial cell dehydrogenase and oxidase, and make it inactive; metal ions in an organic chelated state are more likely to approach the cell, and can interact with microbial cell activity The groups form a bonding relationship, so that the microorganisms cannot reproduce or even die. The two effects may exist in a synergistic effect. At the same time, natural organic acid radicals maintain a weakly alkaline environment, alginic acid has moisturizing properties, and the selected metal ions are life elements. The synergy of the three can make the feed have anti-biotic, disease-preventive, and nutritional supplements, and have better economic benefits.

本发明天然有机酸根褐藻氨酸螯合物作为抗生营养素的应用,其在实施例中的实验结果也得到了相应证实,与传统抗生营养素相比,本发明天然有机酸根褐藻氨酸是海洋天然非蛋白氨基酸,与生物必需金属元素形成的螯合物也是环境友好型抗生素,为充分利用这一宝贵海洋天然生物活性物质开拓了新的用途方向。The application of the natural organic acid radical fucoidic acid chelate of the present invention as an antibiotic nutrient has also been confirmed by the experimental results in the examples. Compared with the traditional antibiotic nutrient, the natural organic acid radical fucoidic acid of the present invention is a marine natural non-toxic nutrient. Proteoamino acids, chelates formed with biologically essential metal elements are also environmentally friendly antibiotics, opening up a new direction of use for making full use of this precious marine natural bioactive substance.

天然有机酸根褐藻氨酸与现有技术中的卤素负离子,硫酸根、硝酸根、磷酸根、醋酸根、氢氧根等无机负离子相比,有更好的生物相容性,可生物降解,无毒副作用、安全性高。Compared with inorganic anions such as halogen anions, sulfate, nitrate, phosphate, acetate, and hydroxide in the prior art, the natural organic acid fucoidin has better biocompatibility, biodegradability, and no Toxic and side effects, high safety.

因此,天然有机酸根褐藻氨酸螯合物具有良好的广谱抗微生物能力和营养供给能力。Therefore, the natural organic acid radical fucoidan chelate has good broad-spectrum antimicrobial ability and nutrient supply ability.

附图说明Description of drawings

下面结合附图对本发明做进一步清楚、完整的说明:Below in conjunction with accompanying drawing, the present invention is further clearly and completely described:

图1为本发明实施例1对大肠杆菌的抑菌圈图及抑菌圈直径d值(抑菌圈法)。Fig. 1 is the bacteriostatic zone figure and bacteriostatic zone diameter d value (inhibition zone method) of the embodiment 1 of the present invention to Escherichia coli.

具体实施方式Detailed ways

本发明公开了一种天然有机酸根褐藻氨酸螯合物作为抗生营养素的应用,为了使本发明的优点、技术方案更加清楚、明确,下面结合具体实施例对本发明做进一步清楚、完整的说明。The present invention discloses the application of a natural organic acid root fucoidin chelate as an antibiotic nutrient. In order to make the advantages and technical solutions of the present invention clearer and clearer, the present invention will be further clearly and completely described below in conjunction with specific examples.

本发明所选原料均可通过商业渠道购买得到。The selected raw materials of the present invention can be purchased through commercial channels.

为了进一步说明本发明的目的,特举以下实施例来说明:In order to further illustrate the purpose of the present invention, the following examples are given to illustrate:

实施例1:Example 1:

抗坏血酸根褐藻氨酸螯合稀土做动物饲料添加剂,占饲料重量百分比例大于或等于1%,小于或等于10%,饲料储存保质期增长6个月,每Kg饲料转化蛋白率增加5.7%,为绿色无公害饲料多效能添加剂。如图1所示,一般抑菌直径大于等于10mm,便为有效抗生剂,此处抑菌圈直径28mm,说明杀菌能力较大。此例证明了抗坏血酸根褐藻氨酸螯合稀土既可防治饲料腐败,又能补充营养、提高饲料转化蛋白率。Ascorbate fucoidan acid chelated rare earth as animal feed additive, the weight percentage of feed is greater than or equal to 1%, less than or equal to 10%, the shelf life of feed storage is increased by 6 months, and the conversion protein rate of feed per Kg is increased by 5.7%, which is green Pollution-free feed multi-effect additive. As shown in Figure 1, generally, the antibacterial diameter is greater than or equal to 10mm, which is an effective antibiotic. Here, the diameter of the antibacterial zone is 28mm, indicating that the antibacterial ability is relatively large. This example proves that ascorbate fucoidin chelated rare earth can not only prevent feed spoilage, but also supplement nutrition and improve feed conversion protein rate.

实施例2:Example 2:

与实施例1不同之处在于,分别将抗坏血酸根负离子替换成柠檬酸根、酒石酸根、马来酸根、月桂酸根、乳酸根、氨基酸根负离子,有同实例1相近的功效。以猪饲料为例,实验结果见表1(空白为未添加功能成分样)。The difference from Example 1 is that the ascorbate anion is replaced by citrate, tartrate, maleate, laurate, lactate, and amino acid anions, which have similar effects to Example 1. Taking pig feed as an example, the experimental results are shown in Table 1 (the blank is a sample without added functional components).

表1不同抗生营养成分的饲用效果1Table 1 Feeding Effect 1 of Different Antibiotic Nutrients

实施例3:Example 3:

与实施例1不同之处在于:分别将稀土离子替换成钙、铁、铜、锌、钴等金属离子,有同实例1相近的功效。以肉食鸡饲料为例,实验结果见表2(空白为未添加功能成分样)。The difference from Example 1 is that the rare earth ions are replaced by metal ions such as calcium, iron, copper, zinc, cobalt, etc., and the effect is similar to that of Example 1. Taking broiler chicken feed as an example, the experimental results are shown in Table 2 (the blank is a sample without added functional components).

表2不同抗生营养成分的饲用效果2Table 2 Feeding Effect 2 of Different Antibiotic Nutrients

实施例4:Example 4:

与实施例1不同之处在于:先将抗坏血酸根褐藻氨酸螯合稀土与L-赖氨酸及抗菌肽按2:1:1重量份数比混合均匀,而后做动物饲料添加剂,占饲料重量百分比例大于或等于1%,小于或等于10%,有同实例1相近的功效。The difference from Example 1 is that: first mix the ascorbate radical fucoidic acid chelated rare earth with L-lysine and antimicrobial peptide evenly at a ratio of 2:1:1 by weight, and then make animal feed additives, accounting for the weight of the feed The percentage example is greater than or equal to 1%, and is less than or equal to 10%, has the similar effect with example 1.

实施例5:Example 5:

与实施例1不同之处在于:将抗坏血酸根负离子替换成氨基酸根负离子,将稀土离子替换成锌离子,有同实例1相近的功效。以猪饲料为例,饲料储层保质期为10个月,每千克饲料转化蛋白率百分率为27.9%。The difference from Example 1 is that the ascorbate anions are replaced by amino acid anions, and the rare earth ions are replaced by zinc ions, which have effects similar to those in Example 1. Taking pig feed as an example, the shelf life of the feed reservoir is 10 months, and the conversion protein rate per kilogram of feed is 27.9%.

本发明制备得到的天然有机酸根褐藻氨酸螯合物具有良好的广谱抗微生物能力和营养供给能力。The natural organic acid root fucoidin chelate prepared by the invention has good broad-spectrum antimicrobial ability and nutrient supply ability.

Claims (3)

1. application of the organic acid laminine chelate as antibiotic nutrient element, the organic acid laminine chelate Molecular formula such as (1-1):
Wherein, Y represents anion when organic acid laminine chelate cation forms crystal, and the anion includes lemon One in lemon acid group, tartrate anion, maleate, laurate, palm acid group, lactate, Vitamin C acid group or amino acid group Kind;
M represents one kind in calcium ion, iron ion, cobalt ions, zinc ion, copper ion or mixed light rare earth ion;The application For antibiotic nutrient feed manufacturing field;The organic acid laminine chelate shared percent by weight in antibiotic nutrient feed Than for 1-10%.
2. application according to claim 1, it is characterised in that:The organic acid laminine chelate adds as feed It is 23.7%-27.4% per kilogram of feed transforming protein rate percentage when adding agent.
3. application according to claim 1, it is characterised in that:The Y is amino acid group, and the M is zinc ion.
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Publication number Priority date Publication date Assignee Title
CN1091430A (en) * 1993-02-16 1994-08-31 北京市潮白河新技术研究所 The preparation method of built amino-acid chelate
CN101304670A (en) * 2005-11-11 2008-11-12 埃德瓦多·沃特·埃特林 Salts of mineral nutrients stabilized with amino acids and/or ammonium salts, products and food supplements containing such salts and process for obtaining such salts
CN101838213A (en) * 2010-07-06 2010-09-22 青岛科技大学 Method for preparing laminine and pharmaceutically acceptable salts thereof

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Title
《昆布氨酸的纯化以及吸湿性、抗菌性研究》;孔合心;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20131215;摘要 *

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