CN111592679A - 一种新型促进乳酸菌生长的纳米水凝胶及其制备方法 - Google Patents

一种新型促进乳酸菌生长的纳米水凝胶及其制备方法 Download PDF

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CN111592679A
CN111592679A CN202010390235.1A CN202010390235A CN111592679A CN 111592679 A CN111592679 A CN 111592679A CN 202010390235 A CN202010390235 A CN 202010390235A CN 111592679 A CN111592679 A CN 111592679A
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张四海
吕耀平
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Abstract

本发明公开了一种新型促进乳酸菌生长的纳米水凝胶及其制备方法，首先将含双膦酸盐的聚合物和蛋黄低密度脂蛋白溶液以及羧甲基淀粉钠混合均匀，在戊二醛作用下反应得到纳米水凝胶；再将纳米水凝胶先后在双膦酸盐缓冲盐溶液和硫酸锰溶液中浸泡，最后得到目标纳米水凝胶。本发明的纳米粒子具有一定空间体积，扩大了菌体生长范围，并且起到了分隔菌体生长的作用；所加入的蛋黄低密度脂蛋白属于纳米级球形大分子物质，含有脂和蛋白，为乳酸菌的生长提供所需营养；此外，纳米水凝胶中添加的锰离子在促进乳酸菌生长方面有明显作用。相较于传统培养乳酸菌的方法，本发明所制的材料不仅提供了菌体立体的生长空间，而且有效的促进菌体生长。

Description

一种新型促进乳酸菌生长的纳米水凝胶及其制备方法
技术领域
本发明属高分子材料领域，涉及一种新型促进乳酸菌生长的纳米水凝胶及其制备方法。
背景技术
乳酸菌不仅是研究生化、遗传、分子生物学和基因工程的理想材料，而且在工业、农牧业、食品和医药等与人类生活密切相关的重要领域具有极高的应用价值。目前，用MRS固体培养基和液体培养基培养是最常见培养乳酸菌的方法，在固体培养基上培养的为平面生长的乳酸菌，菌落较小，生长缓慢且生长环境受限；而乳酸菌在液体发酵培养基内可以很快的生长，但在生长过程中缺少可依附的载体，菌体大部分处于游离的状态，最后收集过程较为繁琐且成本较高。此外乳酸菌的生长需要微量元素的供给，例如锰离子，但是简单人工添加很难控制量，而依托自动化设备添加成本较高。脂和蛋白也是促进乳酸菌生长的重要营养成分，目前载体制备上材料多为石油基聚烯烃衍生物，以脂和蛋白为作为原料制备载体主体骨架和关键包埋物的报道较少。因此，若能研制出一种可促进乳酸菌生长的载体材料，在提供较全面营养物质的同时又具有缓慢供给微量元素的功能就具有十分重要的意义。
发明内容
本发明的目的在于克服现有技术中乳酸菌培养方法中乳酸菌生长空间不足，生长缓慢，没有可依附的载体以及微量元素添加控制难等问题。针对这系列问题，开发了一种新型促进乳酸菌生长的纳米水凝胶，选择可吸附锰离子的含双膦酸盐的聚合物、蛋黄低密度脂蛋白及羧甲基淀粉钠作为制备水凝胶的原料；通过这三种原料与其他原料反应后得到一种可促进乳酸菌生长的新型促进乳酸菌生长的羧甲基淀粉钠的纳米水凝胶。
为解决其技术问题，本发明采用的技术方案为：
一种新型促进乳酸菌生长的纳米水凝胶的制备方法，首先合成具有锰离子吸附功能的含双膦酸盐的聚合物，再通过高速剪切法溶解得到蛋黄低密度脂蛋白溶液和羧甲基淀粉钠，最后将上述两步得到的物质混合均匀，在戊二醛作用下反应得到纳米水凝胶；将纳米水凝胶浸置在含有促进乳酸菌生长物质的含锰离子溶液中，然后冷冻干燥，即得促进乳酸菌生长的纳米水凝胶。
具体步骤如下：
(1)将1-10g的丙烯酸酯双膦酸盐、1-10g甲基丙烯酸羟乙酯、1-10ml丙烯酸及0.1-1.6g的偶氮二异丁腈溶解到60-150ml无水四氢呋喃、乙醇或甲醇中，在氮气保护下反应15-30min，然后将反应瓶置于60-90℃的油浴锅中反应6-24h，并冷凝回流，反应完成后进行减压蒸馏除去溶剂和未反应的单体，即得含双膦酸盐盐的聚合物；
(2)将1-15g的蛋黄低密度脂蛋白通过高速剪切的方法溶解在10-100ml 去离子水中，制得蛋黄低密度脂蛋白溶液；
(3)将1-30g的羧甲基淀粉钠通过高速剪切的方法溶解在10-100ml去离子水中，得到羧甲基淀粉钠溶液；
(4)称取步骤(1)制得的含双膦酸盐盐的聚合物1-10g和步骤(3)制得的羧甲基淀粉钠溶液1-10ml加入到步骤(2)制得的1-5ml蛋黄低密度脂蛋白溶液中剧烈搅拌20-30h，然后在200-300rpm的搅拌下，将混合物通过注射器滴入 20-40ml含5-10wt％硼酸的丙酮溶液中，滴加完毕后溶液陈化20-25h，再向混合物中加入1-6ml戊二醛和1mol/L的盐酸1-5ml，在40-60℃下孵育7-10h，即得纳米水凝胶；
(5)通过浸渍法将步骤(4)得到的纳米水凝浸泡在3-10wt％100-500ml硫酸锰、二氯化锰或硝酸锰溶液中1-10h，再用乙醇洗去水凝胶表面游离的离子和未吸附的离子，冷冻干燥即得促进乳酸菌生长的纳米水凝胶。
所述步骤(1)中丙烯酸酯双膦酸盐的制备步骤如下：将0.1-1mol N-丙烯酰氧基琥珀酰亚胺和0.01-0.1mol帕米膦酸二钠盐一起溶解在100-1000ml pH＝8.0 的NaOH溶液中进行搅拌反应；在室温下反应12-48h后，加入无水乙醇，离心收集沉淀物，用无水乙醇洗涤数次得到丙烯酸酯双膦酸盐。
一种上述制备方法制得的新型促进乳酸菌生长的纳米水凝胶。
本发明相对于现有技术具有的有益效果：
1、本发明借助适宜的纳米水凝胶本体作为载体为菌体生长提供有利的生长空间、微环境。此外因体积较小且无毒不需在乳酸菌收集时进行专门处理，操作性较好。
2、本发明所用的蛋黄低密度脂蛋白作为原料不仅使得载体直接具有为乳酸菌的生长提供所需的蛋白和脂的功能，而且代替了目前作为载体原料的石油基聚烯烃衍生物，方便了原料来源，节约了不可再生的石油资源。
3、本发明可实现锰离子可控缓慢释放，这可为乳酸菌的生长提供微量元素，促进其生长。
具体实施方式
下面结合具体实施方式对本发明作更进一步的举例说明。
实施例1
一种新型促进乳酸菌生长的纳米水凝胶的制备方法，包括以下几个步骤：
1)将0.1mol N-丙烯酰氧基琥珀酰亚胺和0.01mol帕米膦酸二钠盐一起溶解在100ml NaOH溶液(pH＝8.0)中并搅拌用于反应。在室温下反应24小时后，加入无水乙醇，离心收集沉淀物，用无水乙醇洗涤数次制得丙烯酸酯双膦酸盐。
2)将1g的丙烯酸酯双膦酸盐、1g甲基丙烯酸羟乙酯、1ml丙烯酸及0.16 克的偶氮二异丁腈溶解到60ml无水四氢呋喃中，在氮气保护下反应20min，然后将反应瓶置于60℃的油浴锅中反应12小时，并冷凝回流，反应完成后进行减压蒸馏除去溶剂和未反应的单体，即得含双膦酸盐盐的聚合物。
3)将1g的蛋黄低密度脂蛋白通过高速剪切的方法溶解在10ml去离子水中，制得蛋黄低密度脂蛋白溶液。
4)将1g的羧甲基淀粉钠通过高速剪切的方法溶解在10ml去离子水中，得到羧甲基淀粉钠溶液。
5)称取1g含双膦酸盐盐的聚合物1g和1ml羧甲基淀粉钠溶液,加入到1ml 蛋黄低密度脂蛋白溶液中剧烈搅拌24h，然后在250rpm的搅拌下，将混合物通过注射器滴入20ml含5wt％硼酸的丙酮溶液中，滴加完毕后溶液陈化24h后，再向混合物中加入1ml戊二醛和1mol/L盐酸1ml，在50℃下孵育8h,即得羟甲基钠纳米水凝胶。
6)通过浸渍法将最后得到的纳米水凝浸泡在5wt％100ml硝酸锰溶液中5h，再用乙醇洗去水凝胶表面游离的离子和未吸附的离子，冷冻干燥，得到最终的促进乳酸菌生长的纳米水凝胶。
实施例2
一种新型促进乳酸菌生长的纳米水凝胶的制备方法，包括以下几个步骤：
1)将0.5mol N-丙烯酰氧基琥珀酰亚胺和0.05mol帕米膦酸二钠盐一起溶解在500ml NaOH溶液(pH＝8.0)中并搅拌用于反应。在室温下反应36小时后，加入无水乙醇，离心收集沉淀物，用无水乙醇洗涤数次制得丙烯酸酯双膦酸盐。
2)将5g的丙烯酸酯双膦酸盐、5g甲基丙烯酸羟乙酯、5ml丙烯酸及0.1 克的偶氮二异丁腈溶解到100ml甲醇中，在氮气保护下反应15min，然后将反应瓶置于80℃的油浴锅中反应18小时，并冷凝回流，反应完成后进行减压蒸馏除去溶剂和未反应的单体，即得含双膦酸盐盐的聚合物。
3)将8g的蛋黄低密度脂蛋白通过高速剪切的方法溶解在50ml去离子水中，制得蛋黄低密度脂蛋白溶液。
4)将15g的羧甲基淀粉钠通过高速剪切的方法溶解在50ml去离子水中，得到羧甲基淀粉钠溶液。
5)称取5g含双膦酸盐盐的聚合物和5ml羧甲基淀粉钠溶液,加入到2ml蛋黄低密度脂蛋白溶液中剧烈搅拌20h，然后在200rpm的搅拌下，将混合物通过注射器滴入30ml含7wt％硼酸的丙酮溶液中，滴加完毕后溶液陈化20h后，再向混合物中加入3ml戊二醛和1mol/L盐酸2ml，在40℃下孵育7h，即得羟甲基钠纳米水凝胶。
6)通过浸渍法将最后得到的纳米水凝浸泡在，3wt％250ml二氯化锰溶液中 1h，再用乙醇洗去水凝胶表面游离的离子和未吸附的离子，冷冻干燥，得到最终促进乳酸菌生长的纳米水凝胶。
实施例3
一种新型促进乳酸菌生长的纳米水凝胶的制备方法，包括以下几个步骤：
1)将0.8mol N-丙烯酰氧基琥珀酰亚胺和0.08mol帕米膦酸二钠盐一起溶解在800ml NaOH溶液(pH＝8.0)中并搅拌用于反应。在室温下反应12小时后，加入无水乙醇，离心收集沉淀物，用无水乙醇洗涤数次制得丙烯酸酯双膦酸盐。
2)将8g的丙烯酸酯双膦酸盐、8g甲基丙烯酸羟乙酯、8ml丙烯酸及1克的偶氮二异丁腈溶解到120ml无水四氢呋喃中，在氮气保护下反应30min，然后将反应瓶置于90℃的油浴锅中反应24小时，并冷凝回流，反应完成后进行减压蒸馏除去溶剂和未反应的单体，即得含双膦酸盐盐的聚合物。
3)将15g的蛋黄低密度脂蛋白通过高速剪切的方法溶解在80ml去离子水中，制得蛋黄低密度脂蛋白溶液。
4)将25g的羧甲基淀粉钠通过高速剪切的方法溶解在80ml去离子水中，得到羧甲基淀粉钠溶液。
5)称取8g含双膦酸盐盐的聚合物和8ml羧甲基淀粉钠溶液,加入到4ml蛋黄低密度脂蛋白溶液中剧烈搅拌30h，然后在300rpm的搅拌下，将混合物通过注射器滴入35ml含8wt％硼酸的丙酮溶液中，滴加完毕后溶液陈化25h后，再向混合物中加入6ml戊二醛和5mol/L盐酸4ml，在60℃下孵育10h，即得羟甲基钠纳米水凝胶。
6)通过浸渍法将最后得到的纳米水凝浸泡在8wt％400ml硫酸锰溶液中8h，再用乙醇洗去水凝胶表面游离的离子和未吸附的离子，冷冻干燥，得到最终促进乳酸菌生长的纳米水凝胶。
实施例4
一种新型促进乳酸菌生长的纳米水凝胶的制备方法，包括以下几个步骤：
1)将1mol N-丙烯酰氧基琥珀酰亚胺和0.1mol帕米膦酸二钠盐一起溶解在1000ml NaOH溶液(pH＝8.0)中并搅拌用于反应。在室温下反应48小时后，加入无水乙醇，离心收集沉淀物，用无水乙醇洗涤数次制得丙烯酸酯双膦酸盐。
2)将10g的丙烯酸酯双膦酸盐、10g甲基丙烯酸羟乙酯、10ml丙烯酸及1.6 克的偶氮二异丁腈溶解到150ml乙醇中，在氮气保护下反应20min，然后将反应瓶置于90℃的油浴锅中反应24小时，并冷凝回流，反应完成后进行减压蒸馏除去溶剂和未反应的单体，即得含双膦酸盐盐的聚合物。
3)将15g的蛋黄低密度脂蛋白通过高速剪切的方法溶解在100ml去离子水中，制得蛋黄低密度脂蛋白溶液。
4)将30g的羧甲基淀粉钠通过高速剪切的方法溶解在100ml去离子水中，得到羧甲基淀粉钠溶液。
5)称取10g含双膦酸盐盐的聚合物10g和10ml羧甲基淀粉钠溶液,加入到 5ml蛋黄低密度脂蛋白溶液5ml中剧烈搅拌30h，然后在250rpm的搅拌下，将混合物通过注射器滴入40ml含10wt％硼酸的丙酮溶液中，滴加完毕后溶液陈化 24h后，再向混合物中加入6ml戊二醛和1mol/L盐酸5ml，在60℃下孵育10h, 即得羟甲基钠纳米水凝胶。
6)通过浸渍法将最后得到的纳米水凝浸泡在10wt％500ml硫酸锰溶液中 10h，再用乙醇洗去水凝胶表面游离的离子和未吸附的离子，冷冻干燥，得到最终促进乳酸菌生长的纳米水凝胶。
对于本领域技术人员而言，显然本发明不限于上述示范性实施例的细节，而且在不背离本发明的精神或基本特征的情况下，能够以其他的具体形式实现本发明。因此，无论从哪一点来看，均应将实施例看作是示范性的，而且是非限制性的，本发明的范围由所附权利要求而不是上述说明限定，因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明内。

Claims (4)

1.一种新型促进乳酸菌生长的纳米水凝胶的制备方法，其特征在于：首先合成具有锰离子吸附功能的含双膦酸盐的聚合物，再通过高速剪切法溶解得到蛋黄低密度脂蛋白溶液和羧甲基淀粉钠，最后将上述两步得到的物质混合均匀，在戊二醛作用下反应得到纳米水凝胶；将纳米水凝胶浸置在含有促进乳酸菌生长物质的含锰离子溶液中，然后冷冻干燥，即得促进乳酸菌生长的纳米水凝胶。
2.根据权利要求1所述的制备方法，包括以下步骤：
(1)将1-10g的丙烯酸酯双膦酸盐、1-10g甲基丙烯酸羟乙酯、1-10ml丙烯酸及0.1-1.6g的偶氮二异丁腈溶解到60-150ml无水四氢呋喃、乙醇或甲醇中，在氮气保护下反应15-30min，然后将反应瓶置于60-90℃的油浴锅中反应6-24h，并冷凝回流，反应完成后进行减压蒸馏除去溶剂和未反应的单体，即得含双膦酸盐盐的聚合物；
(2)将1-15g的蛋黄低密度脂蛋白通过高速剪切的方法溶解在10-100ml去离子水中，制得蛋黄低密度脂蛋白溶液；
(3)将1-30g的羧甲基淀粉钠通过高速剪切的方法溶解在10-100ml去离子水中，得到羧甲基淀粉钠溶液；
(4)称取步骤(1)制得的含双膦酸盐盐的聚合物1-10g和步骤(3)制得的羧甲基淀粉钠溶液1-10ml加入到步骤(2)制得的1-5ml蛋黄低密度脂蛋白溶液中剧烈搅拌20-30h，然后在200-300rpm的搅拌下，将混合物通过注射器滴入20-40ml含5-10wt％硼酸的丙酮溶液中，滴加完毕后溶液陈化20-25h，再向混合物中加入1-6ml戊二醛和1mol/L的盐酸1-5ml，在40-60℃下孵育7-10h，即得纳米水凝胶；
(5)通过浸渍法将步骤(4)得到的纳米水凝浸泡在3-10wt％100-500ml硫酸锰、二氯化锰或硝酸锰溶液中1-10h，再用乙醇洗去水凝胶表面游离的离子和未吸附的离子，冷冻干燥即得促进乳酸菌生长的纳米水凝胶。
3.根据权利要求2所述的制备方法，其特征在于：所述步骤(1)中丙烯酸酯双膦酸盐的制备步骤如下：将0.1-1mol N-丙烯酰氧基琥珀酰亚胺和0.01-0.1mol帕米膦酸二钠盐一起溶解在100-1000ml pH＝8.0的NaOH溶液中进行搅拌反应；在室温下反应12-48h后，加入无水乙醇，离心收集沉淀物，用无水乙醇洗涤数次得到丙烯酸酯双膦酸盐。
4.一种根据权利要求1-3任一所述的制备方法制得的新型促进乳酸菌生长的纳米水凝胶。
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