CN112915974A - 苹果酸-壳聚糖纳米孔水凝胶微球及其制备方法及应用 - Google Patents
苹果酸-壳聚糖纳米孔水凝胶微球及其制备方法及应用 Download PDFInfo
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Abstract
本发明公开了苹果酸‑壳聚糖纳米孔水凝胶微球及其制备方法及应用,属于保障水产食品安全,制备麻痹性贝类毒素生物吸附剂的技术领域;本发明公开了的苹果酸‑壳聚糖纳米孔水凝胶微球的制备方法具体包括:将苹果酸与壳聚糖制成水凝胶;再将制得的水凝胶中加入纳米二氧化硅和甘油,添加氢氧化钠,在碱性条件下纳米二氧化硅完全溶解后形成分布均匀的纳米孔,经洗涤、冷冻干燥以及研磨过筛制得苹果酸‑壳聚糖纳米孔水凝胶微球;本发明制备的苹果酸‑壳聚糖纳米孔水凝胶微球可以作为高效吸附剂,对水体中麻痹性贝类毒素进行吸附脱除。本发明公开的制备方法简单,使用方便,干燥后易于保存,对贝类毒素污染以及提高产品的安全性具有重大的应用意义。
Description
技术领域
本发明涉及保障水产食品安全,制备麻痹性贝类毒素生物吸附剂的技术领域,特别是涉及苹果酸-壳聚糖纳米孔水凝胶微球及其制备方法及应用。
背景技术
麻痹性贝类毒素主要来源于双鞭甲藻类、淡水蓝藻或有害藻的共生菌,为一类海洋生物膜神经毒素,特异性阻断神经细胞膜上Na+通道引起麻痹,甚至死亡。滤食性贝类、某些鱼类等摄食毒藻,毒素在体内不断累积,可经食物链传递到人类,对公共安全、人体健康和海洋经济构成严重威胁。目前尚无有效的解毒剂或药物治疗麻痹性贝类中毒。为了降低麻痹性贝毒对人类的危害,开发吸附量大且成本较低的高效吸附剂就显得尤为重要。
壳聚糖含有氨基和羟基,成为生物吸附剂的高分子候选材料,用于去除重金属离子或毒素。壳聚糖无毒,不产生二次污染,可通过生物分解代谢分解。但该材料也存在酸稳定性差,孔隙率低,比表面积低的问题,极大地限制了它的应用。为了提高材料的吸附能力,应用物理和化学交联改性方法,增加材料的孔隙率和吸附位点的数量,具有很大的去除毒素的潜力。苹果酸存在于大多数生物体的新陈代谢中。它作为一种强抗氧化剂和螯合剂在食品工业中得到了广泛的应用,具有作为一种理想的壳聚糖水凝胶微球前体的巨大潜力。在壳聚糖水凝胶微球的吸附中,静电吸引或离子交换反应、螯合反应被认为是主要途径,提高了壳聚糖的吸附性能。
目前以壳聚糖和苹果酸为候选材料对水体中麻痹性贝类毒素进行吸附脱除的高效吸附剂还未见报道。
发明内容
本发明的目的是提供苹果酸-壳聚糖纳米孔水凝胶微球及其制备方法及应用,以解决上述现有技术存在的问题。
为实现上述目的,本发明提供了如下方案:
本发明提供一种苹果酸-壳聚糖纳米孔水凝胶微球的制备方法,具体步骤包括:
(1)将苹果酸与壳聚糖制成水溶胶;
(2)在步骤(1)制得的水溶胶中加入纳米二氧化硅和甘油,在纳米二氧化硅完全溶解后,经洗涤、冷冻干燥以及研磨过筛制得苹果酸-壳聚糖纳米孔水凝胶微球。
进一步地,步骤(1)所述水溶胶制备的具体过程为:
将苹果酸与壳聚糖混合后,将得到的混合物先加入纯水配制成分散液,再在室温下剧烈搅拌形成均匀的水溶胶。
进一步地,所述苹果酸与壳聚糖的质量比为1:3~1:6。
进一步地,所述分散液中苹果酸与壳聚糖混合物的质量分数为0.5~2.5%。
进一步地,步骤(2)所述纳米二氧化硅的质量分数为0.2~0.8%,甘油的质量分数为0.5~1.5%。
进一步地,步骤(2)所述过筛时所用筛子的规格为100目筛。
进一步地,所述纳米二氧化硅溶解的具体步骤为:
在步骤(1)制得的水溶胶中加入纳米二氧化硅和甘油,经搅拌以及超声处理后,将得到的均匀溶胶滴加到温度为60~100℃的NaOH溶液中溶解纳米二氧化硅。
进一步地,所述超声处理时间为1~3h。
进一步地,所述NaOH溶液的质量分数为8~12%。
本发明还提供一种所述苹果酸-壳聚糖纳米孔水凝胶微球的制备方法制得的苹果酸-壳聚糖纳米孔水凝胶微球。
本发明还提供一种所述的苹果酸-壳聚糖纳米孔水凝胶微球在脱除水体中麻痹性贝类毒素的应用。
本发明公开了以下技术效果:
本发明制备的苹果酸-壳聚糖纳米孔水凝胶微球(SiO2-MA-CS)对麻痹性贝类毒素的脱毒率达到了92.71%,MA-CS对麻痹性贝类毒素的脱毒率为54.31%,SiO2-MA-CS的脱毒效果是明显优于MA-CS。
本发明制备的苹果酸-壳聚糖纳米孔水凝胶微球可以作为高效吸附剂,对水体中麻痹性贝类毒素进行吸附脱除;本发明公开的制备方法简单,使用方便,干燥后易于保存,可以适用于水溶液中贝类毒素的脱除,对贝类毒素污染,提高产品的安全性,具有重大的应用意义。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动性的前提下,还可以根据这些附图获得其他的附图。
图1为本发明苹果酸-壳聚糖纳米孔水凝胶微球的合成示意图;
图2为CS、MA-CS、SiO2-MA-CS的红外光谱图;
图3为放大10000倍的CS、MA-CS和SiO2-MA-CS的扫描电镜图;
图4为CS、MA-CS、SiO2-MA-CS的XRD谱图;其中A为CS,B为MA-CS,C为SiO2-MA-CS;
图5为水凝胶微球对水溶液中麻痹性贝类毒素的吸附结果。
具体实施方式
现详细说明本发明的多种示例性实施方式,该详细说明不应认为是对本发明的限制,而应理解为是对本发明的某些方面、特性和实施方案的更详细的描述。
应理解本发明中所述的术语仅仅是为描述特别的实施方式,并非用于限制本发明。另外,对于本发明中的数值范围,应理解为还具体公开了该范围的上限和下限之间的每个中间值。在任何陈述值或陈述范围内的中间值以及任何其他陈述值或在所述范围内的中间值之间的每个较小的范围也包括在本发明内。这些较小范围的上限和下限可独立地包括或排除在范围内。
除非另有说明,否则本文使用的所有技术和科学术语具有本发明所述领域的常规技术人员通常理解的相同含义。虽然本发明仅描述了优选的方法和材料,但是在本发明的实施或测试中也可以使用与本文所述相似或等同的任何方法和材料。本说明书中提到的所有文献通过引用并入,用以公开和描述与所述文献相关的方法和/或材料。在与任何并入的文献冲突时,以本说明书的内容为准。
在不背离本发明的范围或精神的情况下,可对本发明说明书的具体实施方式做多种改进和变化,这对本领域技术人员而言是显而易见的。由本发明的说明书得到的其他实施方式对技术人员而言是显而易见得的。本申请说明书和实施例仅是示例性的。
关于本文中所使用的“包含”、“包括”、“具有”、“含有”等等,均为开放性的用语,即意指包含但不限于。
实施例1苹果酸-壳聚糖纳米孔水凝胶微球制备方法
(1)将苹果酸与壳聚糖(脱乙酰度90%)按照质量比1:3混合,将混合物加入纯水配制成质量分数为1.5%的分散液,在室温下剧烈搅拌4h,形成均匀的苹果酸-壳聚糖水溶胶。
(2)在步骤(1)所述水溶胶中加入质量分数为0.4%的纳米二氧化硅和质量分数为1.0%的甘油,室温下搅拌2h,超声处理2h,将得到的均匀溶胶滴加到质量分数为10%NaOH溶液中,在80℃保持2h以溶解二氧化硅颗粒并产生多孔结构。最后,用蒸馏水洗涤以除去剩余的NaOH,冷冻干燥后研磨过100目筛子,收集置于干燥器中存放,如图1所示为苹果酸-壳聚糖纳米孔水凝胶微球的合成示意图。
实施例2苹果酸-壳聚糖纳米孔水凝胶微球制备方法
(1)将苹果酸与壳聚糖(脱乙酰度90%)按照质量比1:4混合,将混合物加入纯水配制成质量分数为0.5%的分散液,在室温下剧烈搅拌4h,形成均匀的苹果酸-壳聚糖水溶胶。
(2)在步骤(1)所述水溶胶中加入质量分数为0.2%的纳米二氧化硅和质量分数为0.5%的甘油,室温下搅拌2h,超声处理1h,将得到的均匀溶胶滴加到质量分数为8%NaOH溶液中,在60℃保持2h以溶解二氧化硅颗粒并产生多孔结构。最后,用蒸馏水洗涤以除去剩余的NaOH,冷冻干燥后研磨过100目筛子,收集置于干燥器中存放。
实施例3苹果酸-壳聚糖纳米孔水凝胶微球制备方法
(1)将苹果酸与壳聚糖(脱乙酰度90%)按照质量比1:5混合,将混合物加入纯水配制成质量分数为1.5%的分散液,在室温下剧烈搅拌4h,形成均匀的苹果酸-壳聚糖水溶胶。
(2)在步骤(1)所述水溶胶中加入质量分数为0.6%的纳米二氧化硅和质量分数为1.0%的甘油,室温下搅拌3h,超声处理2h,将得到的均匀溶胶滴加到质量分数为10%NaOH溶液中,在80℃保持1h以溶解二氧化硅颗粒并产生多孔结构。最后,用蒸馏水洗涤以除去剩余的NaOH,冷冻干燥后研磨过100目筛子,收集置于干燥器中存放。
实施例4苹果酸-壳聚糖纳米孔水凝胶微球制备方法
(1)将苹果酸与壳聚糖(脱乙酰度90%)按照质量比1:6混合,将混合物加入纯水配制成质量分数为2.5%的分散液,在室温下剧烈搅拌4h,形成均匀的苹果酸-壳聚糖水溶胶。
(2)在步骤(1)所述水溶胶中加入质量分数为0.8%的纳米二氧化硅和质量分数为1.5%的甘油,室温下搅拌4h,超声处理3h,将得到的均匀溶胶滴加到质量分数为12%NaOH溶液中,在100℃保持3h以溶解二氧化硅颗粒并产生多孔结构。最后,用蒸馏水洗涤以除去剩余的NaOH,冷冻干燥后研磨过100目筛子,收集置于干燥器中存放。
实施例5苹果酸-壳聚糖纳米孔水凝胶微球结构表征
将实施例1中未经处理的壳聚糖(Chitosan,CS,脱乙酰度80%以上,食用级)、实施例1所述步骤(1)制得的MA-CS(苹果酸-壳聚糖水溶胶,MA-CS)以及实施例1最终制得的SiO2-MA-CS(苹果酸-壳聚糖纳米孔水凝胶微球)分别进行结构表征的检测。
(1)红外光谱
如图2所示,FT-IR光谱中壳聚糖(CS)引起的主要峰值中,-OH和-NH2的伸缩振动吸收峰在3442cm-1处,-CH的伸缩振动吸收峰在2920cm-1处,酰胺谱带的在1637cm-1处,-NH2的弯曲振动吸收峰在1616cm-1处,-CH的弯曲振动吸收峰在1383cm-1处,C3-OH中的C-O伸缩振动吸收峰在1078cm-1处,C6-OH中的C-O伸缩振动吸收峰在1030cm-1处,氨基葡糖环的伸缩振动吸收峰在895cm-1处。
物理交联反应(形成MA-CS)后,在1637cm-1和1616cm-1处,CS的峰值分别轻微地向1635cm-1和1629cm-1移动,这表明壳聚糖基质中的-NH2基团与苹果酸基质中的-COOH基团相互作用。
SiO2-MA-CS的FT-IR光谱中出现了Si-O-Si(466cm-1)的增强特征带。但是,壳聚糖本身并未在该区域中强烈吸收。此外,SiO2-MA-CS中观察到在798cm-1处出现了一个新的峰值,对应于硅的特征吸收峰。结果表明,纳米二氧化硅被成功地引入MA-CS中。
(2)扫描电镜
如图3所示,与CS、MA-CS相比较,SiO2-MA-CS的表面粗糙度增加,可见明显的网络状结构,纳米二氧化硅的添加使吸附剂(苹果酸-壳聚糖纳米孔水凝胶微球)的孔隙率进一步增强,且增大了吸附的比表面积。
(3)XRD
如图4所示,CS的第一个峰约在20,归因于壳聚糖的稠状结晶构象,MA-CS及SiO2-MA-CS的XRD图谱没有明显的峰,只有一个中心在20°的宽峰通常伴随着多糖的衍射。同样的,峰值在20的衍射角的差异可能与CS/MA/SiO2共混物脱乙酰度的差异和复合方式的差异有关。结果表明,SiO2-MA-CS的衍射峰明显变宽,这是由于在SiO2-MA-CS形成过程中,聚合物内部结晶部分发生了部分重组所致。当在MA-CS共混体系中加入少量SiO2时,SiO2主峰的缺失可能是由于SiO2含量较低导致MA-CS共混基体的掩蔽效应所致。
实施例6苹果酸-壳聚糖纳米孔水凝胶微球对麻痹性贝类毒素的吸附作用
麻痹性贝类毒素的检测采用GB5009.213-2016酶联免疫吸附法,将10克均质的蓄毒牡蛎肉样品,加入70mL 0.1mol/L的盐酸溶液,煮沸并搅拌5分钟,6000r/min离心10分钟,取上清液用于检测。利用酶联免疫吸附试验法测定处理前后麻痹性贝类毒素的含量,根据公式∶脱毒率%=(未处理的毒素含量-处理后的毒素含量)×100%/未处理的毒素含量,计算脱毒率。
如图5所示,SiO2-MA-CS对麻痹性贝类毒素的脱毒率达到了92.71%,MA-CS对麻痹性贝类毒素的脱毒率为54.31%,SiO2-MA-CS的脱毒效果是明显优于MA-CS。
由此可知,本发明制备的苹果酸-壳聚糖纳米孔水凝胶微球可以作为高效吸附剂,对水溶液中麻痹性贝类毒素进行吸附脱除。
以上所述的实施例仅是对本发明的优选方式进行描述,并非对本发明的范围进行限定,在不脱离本发明设计精神的前提下,本领域普通技术人员对本发明的技术方案做出的各种变形和改进,均应落入本发明权利要求书确定的保护范围内。
Claims (10)
1.一种苹果酸-壳聚糖纳米孔水凝胶微球的制备方法,其特征在于,具体步骤包括:
(1)将苹果酸与壳聚糖制成水溶胶;
(2)在步骤(1)制得的水溶胶中加入纳米二氧化硅和甘油,搅拌分散均匀后,添加氢氧化钠,在碱性条件下纳米二氧化硅溶解后形成均匀分布的纳米孔,经洗涤、冷冻干燥以及研磨过筛制得苹果酸-壳聚糖纳米孔水凝胶微球。
2.根据权利要求1所述的制备方法,其特征在于:步骤(1)所述水溶胶制备的具体过程为:
将苹果酸与壳聚糖混合后,将得到的混合物加入纯水配制成分散液,再在室温下搅拌形成水溶胶。
3.根据权利要求2所述的制备方法,其特征在于:所述苹果酸与壳聚糖的质量比为1:3~1:6。
4.根据权利要求2所述的制备方法,其特征在于,所述分散液中苹果酸与壳聚糖混合物的质量分数为0.5~2.5%。
5.根据权利要求1所述的制备方法,其特征在于:步骤(2)所述纳米二氧化硅的质量分数为0.2~0.8%,甘油的质量分数为0.5~1.5%。
6.根据权利要求1所述的制备方法,其特征在于:步骤(2)中所述纳米二氧化硅溶解的具体步骤为:
在步骤(1)制得的水溶胶中加入纳米二氧化硅和甘油,经搅拌以及超声处理后,将得到的均匀溶胶滴加到温度为60~100℃的NaOH溶液中溶解纳米二氧化硅。
7.根据权利要求6所述的制备方法,其特征在于:所述超声处理时间为1~3h。
8.根据权利要求6所述的制备方法,其特征在于:所述NaOH溶液的质量分数为8~12%。
9.一种权利要求1~8任一项所述苹果酸-壳聚糖纳米孔水凝胶微球的制备方法制得的苹果酸-壳聚糖纳米孔水凝胶微球。
10.一种权利要求9所述的苹果酸-壳聚糖纳米孔水凝胶微球在脱除水体中麻痹性贝类毒素的应用。
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