CN110655673B - 一种pH和盐离子双重响应的多孔淀粉微凝胶的制备方法 - Google Patents
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Abstract
本发明属于淀粉深加工技术领域,公开了一种pH和盐离子双重响应的多孔淀粉微凝胶的制备方法。本发明以玉米淀粉为原料,采用TEMPO氧化法和酶解法制备对淀粉进行改性,然后利用三偏磷酸钠做交联剂,制备淀粉微凝胶,吸附阴离子营养素。采用该方法制备的微凝胶具有很好的吸附阴离子营养素的能力。
Description
技术领域
本发明属于淀粉深加工技术领域,本发明涉及一种pH和盐离子双重响应的多孔淀粉微凝胶的制备方法。
背景技术
天然营养素是一类重要的功能性食品原料,具有抗氧化、调节生理机能、延缓衰老、预防慢性疾病等有益人体健康的功能特性,但其对环境因素敏感、结构不稳定、易被体内消化酶降解等缺陷,极大限制了营养素的实际应用。
淀粉具有来源广泛、生物可降解、生物相容性好、成本低等特点,在营养载体构建方面展现出独特优势。但是,天然淀粉本身只具有微弱的吸附性能,依赖颗粒表面原子或原子团的微弱化合价产生的吸引力来进行吸附化合物,当被吸附物受到外界更大的吸引力时,就会逐渐脱离,无法达到吸附的目的,因此,需要对天然淀粉进行改性来增大其吸附效果。
但以淀粉为原料,构筑多孔结构敏感型微凝胶的研究还未见报道。
发明内容
为了克服现有技术的不足,本发明目的在于提供一种表面负电荷分布的pH和盐离子双重响应的多孔淀粉微凝胶的制备方法,用以吸附阳离子营养素;本发明以玉米淀粉为原料,采用2.2.6.6-四甲基哌啶TEMPO氧化法和酶解法制备对淀粉进行改性,然后利用三偏磷酸钠做交联剂,制备多孔淀粉微凝胶,吸附阳离子营养素。采用该方法制备的微凝胶具有很好的吸附阳离子营养素的能力。
本发明的上述目的是通过以下技术方案实现的:
一种pH和盐离子双重响应的多孔淀粉微凝胶的制备方法;
S1.氧化淀粉制备:将1g玉米淀粉悬浮在30-60mL水中,然后添加20-40mg TEMPO和200-400mg NaBr。然后将每个反应体系在20-25℃下调节至pH值为10,并向反应中加入2-4mL NaClO溶液,用NaOH调节反应体系pH为10。反应结束后,加入8-12mL乙醇终止反应。然后,将溶液调节到pH为6,用乙醇洗涤沉淀,35-45℃烘干,得到氧化淀粉。
S2.酶解氧化淀粉制备:用醋酸钠缓冲液(pH=4)将氧化淀粉配置成质量浓度20-30%的溶液,加入糖化酶,酶与淀粉的比例为1:80-120(w/w),40℃条件下反应2-4h,加入氢氧化钠溶液停止水解,加入乙醇沉淀,10000转/分,离心3-6min,将离心得到的沉淀用乙醇洗涤三次,35-45℃烘干,得到酶解氧化淀粉。
S3.多孔淀粉微凝胶制备:取1-2g酶解氧化淀粉,加入0.1-0.4g三偏磷酸钠、0.03-0.1g氢氧化钠、3-6mL去离子水,混匀后35-45℃水浴50-70min,然后置于4℃冰箱中放置20-26h,制备得到多孔淀粉微凝胶。无水乙醇清洗三次,干燥后过200目塞,得到多孔淀粉微凝胶粉末。
本发明与现有技术相比的有益效果是:
天然淀粉只带有微弱的电荷,吸附阳离子营养素的能力较弱,采用本发明提供的制备方法制备的多孔淀粉微凝胶不仅表面具有负电荷,而且其内部具有多孔结构,可以通过表面的静电吸引力和内部的分子包裹力来吸附带正电荷的营养素,因而增加了对阳离子化合物的吸附能力。
附图说明
图1为淀粉扫描电子显微镜图。其中(a)为改性前玉米淀粉,(b)为实施例1多孔淀粉微凝胶。
图2为不同pH条件下多孔淀粉微凝胶吸附花色苷能力的测定图。
图3为不同盐离子条件下多孔淀粉微凝胶吸附花色苷能力的测定图。
具体实施方式
下面通过具体实施例详述本发明,但不限制本发明的保护范围。如无特殊说明,本发明所采用的实验方法均为常规方法,所用实验器材、材料、试剂等均可从商业途径获得。
实施例1
一种pH和盐离子双重响应的多孔淀粉微凝胶的制备方法;
S1.氧化淀粉制备:将1g玉米淀粉悬浮在50mL水中,然后添加32mg TEMPO和320mgNaBr。然后将每个反应体系在25℃下调节至pH值为10,并向反应中加入3mL NaClO溶液,用NaOH调节反应体系pH为10。反应结束后,加入10mL乙醇终止反应。然后,将溶液调节到pH为6,用乙醇洗涤沉淀,40℃烘干,得到氧化淀粉。
S2.酶解氧化淀粉制备:用醋酸钠缓冲液(pH=4)将氧化淀粉配置成质量浓度为25%的溶液,加入糖化酶,酶与淀粉的比例为1:100(w/w),40℃条件下反应4h,加入氢氧化钠溶液停止水解,加入乙醇沉淀,10000转/分,离心5min,将离心得到的沉淀用乙醇洗涤三次,40℃烘干,得到酶解氧化淀粉。
S3.多孔淀粉微凝胶制备:取2g酶解氧化淀粉,加入0.2g三偏磷酸钠、0.3g氢氧化钠、6mL去离子水,混匀后40℃水浴1h,然后置于4℃冰箱中放置24h,制备得到多孔淀粉微凝胶。无水乙醇清洗三次,干燥后过200目塞,得到多孔淀粉微凝胶粉末。玉米淀粉颗粒呈不规则的球形或多面体结构,而经过酶解交联后玉米淀粉失去原有的球形或多面体结构,呈现团块状,并且表面布满微小孔洞。
玉米淀粉颗粒(图1a)呈不规则的椭圆形、球形或多边形结构。玉米淀粉经TEMPO氧化和酶解,再经过交联剂交联后可以制得微凝胶,其表面呈现高度密集的多孔三维结构(图1b)
对得到的多孔淀粉微凝胶的吸附性质进行测定:
称取10mg制备的不同种类微凝胶,加入到选定pH值的9mL磷酸盐缓冲液中,低功率超声10min后,1200W下超声3s,使微凝胶充分的溶胀和分散。加入1mL高浓度花色苷溶液,在室温下低转速搅拌2h,吸附后12000rpm离心5min,取上层液体测量花色苷的浓度,计算花色苷的吸附量。
从图2可以看出,pH值会影响微凝胶对花色苷的吸附量,吸附量随着pH值得增加呈现先减小再增加的趋势,在pH值为3时,吸量达到最低值。
盐浓度对微凝胶的电荷有一定的屏蔽作用,从图3中可以看出,随着盐浓度的增加,微凝胶对花色苷的吸附呈现逐渐减少的趋势。
实施例2
一种pH和盐离子双重响应的多孔淀粉微凝胶的制备方法;
S1.氧化淀粉制备:将1g玉米淀粉悬浮在30mL水中,然后添加20mg TEMPO和200mgNaBr。然后将每个反应体系在20℃下调节至pH值为10,并向反应中加入2mL NaClO溶液,用NaOH调节反应体系pH为10。反应结束后,加入8mL乙醇终止反应。然后,将溶液调节到pH为6,用乙醇洗涤沉淀,35℃烘干,得到氧化淀粉。
S2.酶解氧化淀粉制备:用醋酸钠缓冲液(pH=4)将氧化淀粉配置成质量浓度20-30%的溶液,加入糖化酶,酶与淀粉的比例为1:80(w/w),40℃条件下反应2h,加入氢氧化钠溶液停止水解,加入乙醇沉淀,10000转/分,离心3min,将离心得到的沉淀用乙醇洗涤三次,45℃烘干,得到酶解氧化淀粉。
S3.多孔淀粉微凝胶制备:取1g酶解氧化淀粉,加入0.1g三偏磷酸钠、0.03g氢氧化钠、3mL去离子水,混匀后35℃水浴50min,然后置于4℃冰箱中放置20h,制备得到多孔淀粉微凝胶。无水乙醇清洗三次,干燥后过200目塞,得到多孔淀粉微凝胶粉末。
实施例3
一种pH和盐离子双重响应的多孔淀粉微凝胶的制备方法;
S1.氧化淀粉制备:将1g玉米淀粉悬浮在60mL水中,然后添加40mg TEMPO和400mgNaBr。然后将每个反应体系在25℃下调节至pH值为10,并向反应中加入4mL NaClO溶液,用NaOH调节反应体系pH为10。反应结束后,加入12mL乙醇终止反应。然后,将溶液调节到pH为6,用乙醇洗涤沉淀,45℃烘干,得到氧化淀粉。
S2.酶解氧化淀粉制备:用醋酸钠缓冲液(pH=4)将氧化淀粉配置成质量浓度30%的溶液,加入糖化酶,酶与淀粉的比例为1:120(w/w),40℃条件下反应4h,加入氢氧化钠溶液停止水解,加入乙醇沉淀,10000转/分,离心6min,将离心得到的沉淀用乙醇洗涤三次,45℃烘干,得到酶解氧化淀粉。
S3.多孔淀粉微凝胶制备:取2g酶解氧化淀粉,加入0.4g三偏磷酸钠、0.1g氢氧化钠、6mL去离子水,混匀后45℃水浴70min,然后置于4℃冰箱中放置26h,制备得到多孔淀粉微凝胶。无水乙醇清洗三次,干燥后过200目塞,得到多孔淀粉微凝胶粉末。
以上所述实施方式仅为本发明的优选实施例,而并非本发明可行实施的全部实施例。对于本领域一般技术人员而言,在不背离本发明原理和精神的前提下对其所作出的任何显而易见的改动,都应当被认为包含在本发明的权利要求保护范围之内。
Claims (1)
1.一种pH和盐离子双重响应的多孔淀粉微凝胶的制备方法,其特征是,以玉米淀粉为原料,采用2.2.6.6-四甲基哌啶TEMPO氧化法和酶解法制备对淀粉进行改性,利用三偏磷酸钠做交联剂,制备多孔淀粉微凝胶;
具体制备步骤为:
S1. 氧化淀粉制备:将1g玉米淀粉悬浮在50mL水中,添加32mg TEMPO和320mg NaBr;将反应体系在25℃下调节至pH值为10,并向反应中加入3mL NaClO溶液,用NaOH调节反应体系pH为10;反应结束后,加入10mL乙醇终止反应;将溶液调节到pH为6,用乙醇洗涤沉淀,40℃烘干,得到氧化淀粉;
S2. 酶解氧化淀粉制备:用醋酸钠缓冲液将氧化淀粉配置成质量浓度25%的溶液,加入糖化酶,酶与淀粉的比例为1:100(w/w),40℃条件下反应4 h,加入氢氧化钠溶液停止水解,加入乙醇沉淀,10000转/分,离心5 min,将离心得到的沉淀用乙醇洗涤三次,40℃烘干,得到酶解氧化淀粉;
S3. 多孔淀粉微凝胶制备:取2 g酶解氧化淀粉,加入0.2g三偏磷酸钠、0.3g氢氧化钠、6 mL去离子水,混匀后40℃水浴60min,然后置于4 ℃冰箱中放置24 h,制备得到多孔淀粉微凝胶;无水乙醇清洗三次,干燥后过200目塞,得到多孔淀粉微凝胶粉末。
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