CN108404873B - 一种纳米氧化铁/壳聚糖磷结合剂制备方法及应用 - Google Patents
一种纳米氧化铁/壳聚糖磷结合剂制备方法及应用 Download PDFInfo
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Abstract
本发明属于生物体内高磷血症磷吸附剂的开发制备及其应用技术领域,涉及一种纳米氧化铁/壳聚糖磷结合剂制备方法及应用。以疏水改性纳米氧化铁用作乳化剂,壳聚糖溶液为水相,煤油为油相,制备水包油Pickering乳液;将Pickering乳液分散在含有Span‑80的石蜡溶液中,制备出均匀稳定的油包水包油乳液,向油包水包油乳液中加入戊二醛溶液,反应、静置;滤去上清液,用无水乙醇和去离子水反复破乳洗涤,抽滤;干燥,得到纳米氧化铁/壳聚糖磷结合剂。该纳米氧化铁/壳聚糖磷结合剂可应用于磷的吸附。本发明制备的磷结合剂具有比表面积大,吸附性能好,稳定性强,对人体无明显毒害作用的特点。
Description
技术领域
本发明属于生物体内高磷血症磷吸附剂的开发制备及其应用技术领域,涉及一种纳米氧化铁/壳聚糖磷结合剂制备方法及应用。
背景技术
肾衰竭患者由于生理代谢能力下降,无法正常吸收和排放磷元素,引起体内磷元素的紊乱,引发高磷血症甚至多并发症,导致器官衰竭而死。临床用钙系、镧系等降磷药物,效果不佳、副作用大且成本过高。
纳米氧化铁Fe2O3本身颗粒细微化,具有极大的比表面积,且对无机磷有着较好的吸附作用,吸附迅速,可以用来吸收胃肠道中的磷酸盐离子,控制磷的积累。但长期直接服用氧化铁会存在毒副作用,对人体产生不良的影响。
为有效利用纳米Fe2O3的磷结合性,并降低其潜在的毒副作用,本发明提出一种用天然壳聚糖包裹纳米Fe2O3的方法,利用纳米Fe2O3吸附磷的特性并结合壳聚糖碱性氨基的正电荷吸附负电荷离子的特点,用于强化肠道磷吸附效果。
本发明避免了纳米Fe2O3的体内长期积累的负作用,同时提高了磷吸附特性,同时该结合剂也可用于吸附负电荷离子,为生物用阴离子结合剂提供了技术参考。
发明内容
为解决上述问题,本发明提供一种纳米氧化铁/壳聚糖磷结合剂制备方法及应用,制备的吸附剂集壳聚糖与纳米氧化铁的优点于一体,具有比表面积大,吸附性能好,稳定性强,对人体无明显毒害等优势。
本发明的技术方案:
一种纳米氧化铁/壳聚糖磷结合剂的制备方法,步骤如下:
(1)壳聚糖溶液作为水相,煤油作为油相,疏水改性纳米氧化铁作为乳化剂,制备水包油Pickering乳液;其中,乳化剂在混合体系中的浓度为6wt%~36wt%,油水比为1:1~1:4;
(2)将步骤(1)得到的水包油Pickering乳液分散在含有Span-80的石蜡溶液中,制备出均匀稳定的油包水包油乳液;其中,Span-80与石蜡溶液的体积比为1.5%~3%,水包油Pickering乳液和石蜡溶液的体积比为1:1~1:4,
(3)在20℃~60℃的温度下,向步骤(2)得到的油包水包油乳液中加入戊二醛溶液,反应1~4小时,静置半小时;滤去上清液,用无水乙醇和去离子水反复破乳洗涤,抽滤;干燥4-8小时,得到直径为5~15μm的复合微球,即纳米氧化铁/壳聚糖磷结合剂。
所述的壳聚糖溶液为质量浓度2~4wt%的壳聚糖与体积浓度为2%的乙酸混合得到的壳聚糖乙酸溶液。
所述的疏水改性纳米氧化铁的粒径范围为20~50nm。
所述的纳米氧化铁/壳聚糖磷结合剂的应用,步骤如下:
磷酸盐溶液,浓度为50~1000mgP/g,调节pH为1~8,温度为37℃;将纳米氧化铁/壳聚糖磷结合剂作为吸附剂,加入到磷酸盐溶液中,每100mL磷酸盐溶液加入0.1~0.4g吸附剂,吸附时间2~4h;过滤得到清液,检测吸附容量。
本发明的有益效果:利用壳聚糖表面有机基团和纳米氧化铁对磷酸阴离子的协同吸附,制备出具有比表面积大,吸附性能好,稳定性强,对人体无明显毒害作用的磷结合剂。
具体实施方式
下面通过实施例详述本发明的技术方案,但本发明的保护范围不限于此。
实施例1:
1.将疏水纳米氧化铁加入煤油中制成质量体积浓度为6wt%的浆料,以与煤油的体积计,搅拌分散使其充分混合均匀。将混合好的物料于逐滴加入到配制好的壳聚糖溶液中,煤油与壳聚糖的体积为1:2,制备出O/W Pickering乳液。将制备的Pickering乳液以1:2的体积分散在含有2%Span-80的石蜡溶液中,制备出均匀稳定的油包水包油(O/W/O)乳液。在20℃的温度下加入一定质量的50%的戊二醛溶液,反应4小时,静置半小时,滤去上清液后再用大量无水乙醇和去离子水反复破乳洗涤几次后,抽滤,置于烘箱中干燥4-8小时,直径为5~15μm的壳聚糖/纳米氧化铁复合微球。
2.将上述制备的微球作为吸附剂加入到要吸附的磷酸盐溶液中,调节pH为1~8,温度为37℃,浓度为1000mgP/g,每次100mL溶液加入0.1g吸附剂,吸附时间4h,然后取溶液过滤得清液,用紫外分光光度计检测吸附容量。
实施例2:
1.将疏水纳米氧化铁加入煤油中制成质量体积浓度为12wt%的浆料,以与煤油的体积计,搅拌分散使其充分混合均匀。将混合好的物料于逐滴加入到配制好的壳聚糖溶液中,煤油与壳聚糖的体积为1:2,制备出O/W Pickering乳液。将制备的Pickering乳液以1:2的体积分散在含有2%Span-80的石蜡溶液中,制备出均匀稳定的油包水包油(O/W/O)乳液。在20℃的温度下加入一定质量的50%的戊二醛溶液,反应4小时,静置半小时,滤去上清液后再用大量无水乙醇和去离子水反复破乳洗涤几次后,抽滤,置于烘箱中干燥4-8小时,直径为5~15μm的壳聚糖/纳米氧化铁复合微球。
2.将上述制备的微球作为吸附剂加入到要吸附的磷酸盐溶液中,调节pH为1~8,温度为37℃,浓度为1000mgP/g,每次100mL溶液加入0.1g吸附剂,吸附时间4h,然后取溶液过滤得清液,用紫外分光光度计检测吸附容量。
实施例3:
1.将疏水纳米氧化铁加入煤油中制成质量体积浓度为18wt%的浆料,以与煤油的体积计,搅拌分散使其充分混合均匀。将混合好的物料于逐滴加入到配制好的壳聚糖溶液中,煤油与壳聚糖的体积为1:2,制备出O/W Pickering乳液。将制备的Pickering乳液以1:2的体积分散在含有2%Span-80的石蜡溶液中,制备出均匀稳定的油包水包油(O/W/O)乳液。在20℃的温度下加入一定质量的50%的戊二醛溶液,反应4小时,静置半小时,滤去上清液后再用大量无水乙醇和去离子水反复破乳洗涤几次后,抽滤,置于烘箱中干燥4-8小时,直径为5~15μm的壳聚糖/纳米氧化铁复合微球。
2.将上述制备的微球作为吸附剂加入到要吸附的磷酸盐溶液中,调节pH为1~8,温度为37℃,浓度为1000mgP/g,每次100mL溶液加入0.1g吸附剂,吸附时间4h,然后取溶液过滤得清液,用紫外分光光度计检测吸附容量。
实施例4:
1.将疏水纳米氧化铁加入煤油中制成质量体积浓度为24wt%的浆料,以与煤油的体积计,搅拌分散使其充分混合均匀。将混合好的物料于逐滴加入到配制好的壳聚糖溶液中,煤油与壳聚糖的体积为1:2,制备出O/W Pickering乳液。将制备的Pickering乳液以1:2的体积分散在含有2%Span-80的石蜡溶液中,制备出均匀稳定的油包水包油(O/W/O)乳液。在20℃的温度下加入一定质量的50%的戊二醛溶液,反应4小时,静置半小时,滤去上清液后再用大量无水乙醇和去离子水反复破乳洗涤几次后,抽滤,置于烘箱中干燥4-8小时,直径为5~15μm的壳聚糖/纳米氧化铁复合微球。
2.将上述制备的微球作为吸附剂加入到要吸附的磷酸盐溶液中,调节pH为1~8,温度为37℃,浓度为1000mgP/g,每次100mL溶液加入0.1g吸附剂,吸附时间4h,然后取溶液过滤得清液,用紫外分光光度计检测吸附容量。
实施例5:
1.将疏水纳米氧化铁加入煤油中制成质量体积浓度为30wt%的浆料,以与煤油的体积计,搅拌分散使其充分混合均匀。将混合好的物料于逐滴加入到配制好的壳聚糖溶液中,煤油与壳聚糖的体积为1:2,制备出O/W Pickering乳液。将制备的Pickering乳液以1:2的体积分散在含有2%Span-80的石蜡溶液中,制备出均匀稳定的油包水包油(O/W/O)乳液。在20℃的温度下加入一定质量的50%的戊二醛溶液,反应4小时,静置半小时,滤去上清液后再用大量无水乙醇和去离子水反复破乳洗涤几次后,抽滤,置于烘箱中干燥4-8小时,直径为5~15μm的壳聚糖/纳米氧化铁复合微球。
2.将上述制备的微球作为吸附剂加入到要吸附的磷酸盐溶液中,调节pH为1~8,温度为37℃,浓度为1000mgP/g,每次100mL溶液加入0.1g吸附剂,吸附时间4h,然后取溶液过滤得清液,用紫外分光光度计检测吸附容量。
本实施例4制备的纳米氧化铁/壳聚糖复合微球在1000mgP/L,pH=3下溶液中对磷的吸附容量可高达60mg/g。
以上实施案例仅用于说明本发明的优选实施方式,但本发明并不限于上述实施方式,在所述领域普通技术人员所具备的知识范围内,本发明的精神和原则之内所作的任何修改、等同替代及改进等,均应视为本申请的保护范围。
Claims (5)
1.一种纳米氧化铁/壳聚糖磷结合剂的制备方法,其特征在于,具体步骤如下:
(1)壳聚糖溶液作为水相,煤油作为油相,疏水改性纳米氧化铁作为乳化剂,制备水包油Pickering乳液;其中,乳化剂在混合体系中的浓度为6wt%~36wt%,油水比为1:1~1:4;
(2)将步骤(1)得到的水包油Pickering乳液分散在含有Span-80的石蜡溶液中,制备出均匀稳定的油包水包油乳液;其中,Span-80在石蜡溶液中的体积浓度为1.5%~3%,水包油Pickering乳液和石蜡溶液的体积比为1:1~1:4,
(3)在20℃~60℃的温度下,向步骤(2)得到的油包水包油乳液中加入戊二醛溶液,反应1~4小时,静置半小时;滤去上清液,用无水乙醇和去离子水反复破乳洗涤,抽滤;干燥4-8小时,得到直径为5~15μm的复合微球,即纳米氧化铁/壳聚糖磷结合剂。
2.根据权利要求1所述的一种纳米氧化铁/壳聚糖磷结合剂的制备方法,其特征在于,所述的壳聚糖溶液为质量浓度2~4wt%的壳聚糖与体积浓度为2%的乙酸混合得到的壳聚糖乙酸溶液。
3.根据权利要求1或2所述的一种纳米氧化铁/壳聚糖磷结合剂的制备方法,其特征在于,所述的疏水改性纳米氧化铁的粒径范围为20~50nm。
4.权利要求1或2所述的纳米氧化铁/壳聚糖磷结合剂的应用,其特征在于,具体步骤如下:
磷酸盐溶液,浓度为50~1000mgP/g,调节pH为1~8,温度为37℃;将纳米氧化铁/壳聚糖磷结合剂作为吸附剂,加入到磷酸盐溶液中,每100mL磷酸盐溶液加入0.1~0.4g吸附剂,吸附时间2~4h;过滤得到清液,检测吸附容量。
5.权利要求3所述的纳米氧化铁/壳聚糖磷结合剂的应用,其特征在于,具体步骤如下:
磷酸盐溶液,浓度为50~1000mgP/g,调节pH为1~8,温度为37℃;将纳米氧化铁/壳聚糖磷结合剂作为吸附剂,加入到磷酸盐溶液中,每100mL磷酸盐溶液加入0.1~0.4g吸附剂,吸附时间2~4h;过滤得到清液,检测吸附容量。
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