淀粉基水凝胶的研究进展

doi:10.16085/j.issn.1000-6613.2021-0099

摘要/Abstract

摘要：

淀粉是一种可再生的天然高分子，具有生物相容性好、可生物降解、无毒等优点，而水凝胶是具有吸水、保水性能的亲水聚合物网络。本文对近5年来淀粉基水凝胶的研究成果进行了归纳总结，以期为科研工作者提供淀粉基水凝胶的最新研究进展。文章分为如下部分：第一部分介绍了淀粉基水凝胶的研究背景；第二部分从淀粉基水凝胶的组成、形成原理、环境响应性等方面进行归纳总结；第三部分重点介绍了淀粉基水凝胶在水体净化、药物缓释、3D打印、农业和再生医学方面的应用。由此可知，目前淀粉基水凝胶在传感器、光电材料等方面的应用研究较少，同时其性能还不能够完全满足实际需求，因此科研工作者需进一步研究淀粉基水凝胶的结构与性能相互作用规律，完善淀粉基水凝胶的制备策略，拓展淀粉基水凝胶的应用范围，同时快速将其商品化及市场化，以产生巨大的经济效益与环境效益。

关键词: 凝胶, 淀粉, 吸附, 载体, 自由基聚合, 刺激响应性

Abstract:

Starch is a kind of renewable natural macromolecule, possessing the advantages of good biocompatibility, biodegradation and non-toxicity, while hydrogel is a hydrophilic polymer network with the properties of water absorption and retention. In order to facilitate the researchers to understand the latest research progress of starch-based hydrogels, this paper summarized the research achievements of starch-based hydrogels in the past five years. This paper was divided into the following sections: The first part introduced the research background of starch-based hydrogels. The second part summarizes properties, formation principle and environmental responsiveness of starch-based hydrogels. The third part focused on the application of starch-based hydrogels in water purification, drug sustained release, 3D printing, agriculture and regenerative medicine. According to the facts mentioned above, there were few studies on the applications of starch-based hydrogels in self-healing materials and optoelectronic materials, and at the same time their performance cannot fully meet actual needs. Therefore, researchers needed to further study the interaction between the function and structure of starch-based hydrogel, improved its preparation strategy, expanded its application scope and quickly made it commercialization and marketization to bring huge economic and environmental benefits.

Key words: gels, starch, adsorption, carrier, radical polymerization, stimulus responsiveness

中图分类号:

TB34

刘玉华, 魏宏亮, 李松茂, 刘子君, 李维坤, 王刚. 淀粉基水凝胶的研究进展[J]. 化工进展, 2021, 40(12): 6738-6751.

LIU Yuhua, WEI Hongliang, LI Songmao, LIU Zijun, LI Weikun, WANG Gang. Research progress of starch - based hydrogels[J]. Chemical Industry and Engineering Progress, 2021, 40(12): 6738-6751.

图/表 8

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淀粉类型	其他材料	制备方法	应用	主要结论	参考文献
可溶淀粉	氧化纤维素纳米纤维	静电作用	用作流变改性剂	纤维素的加入提高水凝胶的刚度和黏度	［3］
玉米淀粉	纤维素纳米晶须	辐射交联	药物缓释	加入纳米晶须后，药物释放时间延长了2.9倍	［11］
原淀粉	纤维素纳米纤维/丙烯酸	原子转移自由基聚合	吸附Cu²⁺	水凝胶最大吸附量为957mg/g	［12］
原淀粉	磁功能化纤维素纳米晶（MCNCs）	酶催化	吸附阳离子染料	加入MCNCs的水凝胶对结晶紫、亚甲基蓝的最大吸附量分别为2500.0mg/g、1428.6mg/g，且表现出良好的可重复性	［13］
原淀粉	羧甲基纤维素	物理交联	药物缓释	在pH为6.8和7.4的磷酸盐缓冲液中，水凝胶在12h的药物释放量最高	［14］
玉米淀粉	壳聚糖	自由基聚合	吸附亚甲基蓝	淀粉/壳聚糖比例为50/50时，溶胀度为120%左右，在5h达到平衡，且对染料吸附效果最好	［15］
玉米淀粉	化学改性天然炭纳米颗粒	物理、化学交联	高吸水性材料	化学改性的碳纳米材料水凝胶的吸水量是纯水凝胶的2倍，为389.9g/g，且保水性为23.1%，是纯水凝胶的3倍	［16］
原淀粉	碳化大豆荚	交联剂交联	吸附萘普生药物和Cr（Ⅵ）	最高溶胀度为500%，对Cr（Ⅵ）和萘普生药物的去除率分别为96.45%、78%	［17］
玉米淀粉	氧化石墨烯	一步法	染料吸附	在石墨烯薄片之间掺入淀粉制备的水凝胶，吸附的染料比石墨烯水凝胶多75%	［18］
马铃薯淀粉	埃洛石纳米管	自由基聚合	肥料缓释	水凝胶溶胀度可达5390%，对尿素缓释放在12h后达到84.6%	［19］
双醛淀粉	N-琥珀酰壳聚糖（SCS）	席夫碱反应	药物缓释	姜黄素释放在2天达到平衡，且SCS的含量显著提高了人牙龈成纤维细胞黏附在水凝胶表面的数量，使水凝胶在组织工程软骨修复等方面有应用潜力	［20］
醛基淀粉	氨基羧甲基壳聚糖	席夫碱反应	用于软组织黏合剂、止血等	通过改变醛和氨基的含量，可以调节水凝胶的成胶时间、溶胀率和机械拉伸性能，其最高拉伸强度可达到（42.73±1.18）kPa	［21］
双醛淀粉	明胶	湿法纺丝法	生物医学	海藻酸盐水凝胶纤维和海藻酸盐/明胶混合水凝胶纤维的线密度值由5.79dtex降至4.14dtex，证明明胶的过量加入会破坏藻酸盐/明胶混合水凝胶纤维的力学性能	［22］
氧化淀粉	CuO	原位自由基聚合	药物缓释	该水凝胶在pH为2.1时的溶胀率低于pH为7.4时的溶胀率，其控释性均随纳米氧化铜含量的增加而增加	［23］
氧化淀粉	ZnO	交联剂交联	抑菌性能	该水凝胶在pH为7时水溶液的溶胀度最大，大约为2700%，用于抑菌时细菌零增长，抑菌圈达到11mm	［24］
戊烯酸功能化淀粉	明胶	交联剂交联	组织再生	交联最少的明胶水凝胶具有最高的成脂分化程度，其取代度为31%，储存模量为14kPa	［25］
呋喃功能化淀粉	石墨烯	Diels-Alder反应	生物医学	加入石墨烯使纳米复合水凝胶的力学性能、抗菌活性得到了显著提高，电导率从1.23×10^-4S/m增加到1.16×10^-3S/m	［26］
肉豆蔻酸功能化淀粉	氧化石墨烯	主客体相互作用	水体净化	制备的纳米复合水凝胶具有明显的、相互连通的三维多孔网络，孔径在亚微米到几微米之间	［27］
可溶淀粉	氧化石墨烯	辐射交联	智能电子设备胶黏剂	具有快速自动自愈能力，离子电导率大约为10.5mS/dm	［28］
淀粉纳米晶体（SNCs）	明胶	物理交联	细胞培养	添加0.5%的SNCs压缩模量从（2.0±0.1）kPa增加至（3.1±0.1）kPa，溶胀率变化不大	［29］
可压性淀粉	埃洛石	偶联法	药物缓释	药物装入埃洛石腔内，而不是将药物嵌入水凝胶网络，可以有效地抑制初始的爆发性释放，且在30min达到平衡	［30］

淀粉类型	其他材料	制备方法	应用	主要结论	参考文献
可溶淀粉	氧化纤维素纳米纤维	静电作用	用作流变改性剂	纤维素的加入提高水凝胶的刚度和黏度	［3］
玉米淀粉	纤维素纳米晶须	辐射交联	药物缓释	加入纳米晶须后，药物释放时间延长了2.9倍	［11］
原淀粉	纤维素纳米纤维/丙烯酸	原子转移自由基聚合	吸附Cu²⁺	水凝胶最大吸附量为957mg/g	［12］
原淀粉	磁功能化纤维素纳米晶（MCNCs）	酶催化	吸附阳离子染料	加入MCNCs的水凝胶对结晶紫、亚甲基蓝的最大吸附量分别为2500.0mg/g、1428.6mg/g，且表现出良好的可重复性	［13］
原淀粉	羧甲基纤维素	物理交联	药物缓释	在pH为6.8和7.4的磷酸盐缓冲液中，水凝胶在12h的药物释放量最高	［14］
玉米淀粉	壳聚糖	自由基聚合	吸附亚甲基蓝	淀粉/壳聚糖比例为50/50时，溶胀度为120%左右，在5h达到平衡，且对染料吸附效果最好	［15］
玉米淀粉	化学改性天然炭纳米颗粒	物理、化学交联	高吸水性材料	化学改性的碳纳米材料水凝胶的吸水量是纯水凝胶的2倍，为389.9g/g，且保水性为23.1%，是纯水凝胶的3倍	［16］
原淀粉	碳化大豆荚	交联剂交联	吸附萘普生药物和Cr（Ⅵ）	最高溶胀度为500%，对Cr（Ⅵ）和萘普生药物的去除率分别为96.45%、78%	［17］
玉米淀粉	氧化石墨烯	一步法	染料吸附	在石墨烯薄片之间掺入淀粉制备的水凝胶，吸附的染料比石墨烯水凝胶多75%	［18］
马铃薯淀粉	埃洛石纳米管	自由基聚合	肥料缓释	水凝胶溶胀度可达5390%，对尿素缓释放在12h后达到84.6%	［19］
双醛淀粉	N-琥珀酰壳聚糖（SCS）	席夫碱反应	药物缓释	姜黄素释放在2天达到平衡，且SCS的含量显著提高了人牙龈成纤维细胞黏附在水凝胶表面的数量，使水凝胶在组织工程软骨修复等方面有应用潜力	［20］
醛基淀粉	氨基羧甲基壳聚糖	席夫碱反应	用于软组织黏合剂、止血等	通过改变醛和氨基的含量，可以调节水凝胶的成胶时间、溶胀率和机械拉伸性能，其最高拉伸强度可达到（42.73±1.18）kPa	［21］
双醛淀粉	明胶	湿法纺丝法	生物医学	海藻酸盐水凝胶纤维和海藻酸盐/明胶混合水凝胶纤维的线密度值由5.79dtex降至4.14dtex，证明明胶的过量加入会破坏藻酸盐/明胶混合水凝胶纤维的力学性能	［22］
氧化淀粉	CuO	原位自由基聚合	药物缓释	该水凝胶在pH为2.1时的溶胀率低于pH为7.4时的溶胀率，其控释性均随纳米氧化铜含量的增加而增加	［23］
氧化淀粉	ZnO	交联剂交联	抑菌性能	该水凝胶在pH为7时水溶液的溶胀度最大，大约为2700%，用于抑菌时细菌零增长，抑菌圈达到11mm	［24］
戊烯酸功能化淀粉	明胶	交联剂交联	组织再生	交联最少的明胶水凝胶具有最高的成脂分化程度，其取代度为31%，储存模量为14kPa	［25］
呋喃功能化淀粉	石墨烯	Diels-Alder反应	生物医学	加入石墨烯使纳米复合水凝胶的力学性能、抗菌活性得到了显著提高，电导率从1.23×10^-4S/m增加到1.16×10^-3S/m	［26］
肉豆蔻酸功能化淀粉	氧化石墨烯	主客体相互作用	水体净化	制备的纳米复合水凝胶具有明显的、相互连通的三维多孔网络，孔径在亚微米到几微米之间	［27］
可溶淀粉	氧化石墨烯	辐射交联	智能电子设备胶黏剂	具有快速自动自愈能力，离子电导率大约为10.5mS/dm	［28］
淀粉纳米晶体（SNCs）	明胶	物理交联	细胞培养	添加0.5%的SNCs压缩模量从（2.0±0.1）kPa增加至（3.1±0.1）kPa，溶胀率变化不大	［29］
可压性淀粉	埃洛石	偶联法	药物缓释	药物装入埃洛石腔内，而不是将药物嵌入水凝胶网络，可以有效地抑制初始的爆发性释放，且在30min达到平衡	［30］

应用领域	制备方法	凝胶组成	污染物	比表面积 /m²·g^-1	孔洞容量 /cm³·g^-1	最大吸附量 /mg·g^-1	参考文献
染料吸附	电旋法	淀粉/聚乙烯醇	亚甲基蓝	24.72	0.0421	400	［52］
	原子转移自由基聚合	木薯淀粉/丙烯酰胺	亚甲基蓝	—	—	1917	［70］
	酶催化	原淀粉/MCNCs	结晶紫、亚甲基蓝	—	—	2500.0、1428.6	［13］
	一步法	玉米淀粉/多孔石墨烯	核壳荧光	45	0.03	1.1069	［18］
金属离子	交联剂交联	原淀粉/生物炭	Cr（Ⅵ）	226.94	9.88	420.13	［17］
	交联剂交联	2-羟基-3-异丙氧基丙基淀粉/海藻酸钠	Cu（Ⅱ）	—	—	25.81	［71］
	辐射交联	木薯淀粉/丙烯酸	Pb（Ⅱ）	—	—	561	［72］
	原子转移自由基聚合	原淀粉/纤维素/丙烯酸	Cu（Ⅱ）	—	—	957	［12］

应用领域	制备方法	凝胶组成	污染物	比表面积 /m²·g^-1	孔洞容量 /cm³·g^-1	最大吸附量 /mg·g^-1	参考文献
染料吸附	电旋法	淀粉/聚乙烯醇	亚甲基蓝	24.72	0.0421	400	［52］
	原子转移自由基聚合	木薯淀粉/丙烯酰胺	亚甲基蓝	—	—	1917	［70］
	酶催化	原淀粉/MCNCs	结晶紫、亚甲基蓝	—	—	2500.0、1428.6	［13］
	一步法	玉米淀粉/多孔石墨烯	核壳荧光	45	0.03	1.1069	［18］
金属离子	交联剂交联	原淀粉/生物炭	Cr（Ⅵ）	226.94	9.88	420.13	［17］
	交联剂交联	2-羟基-3-异丙氧基丙基淀粉/海藻酸钠	Cu（Ⅱ）	—	—	25.81	［71］
	辐射交联	木薯淀粉/丙烯酸	Pb（Ⅱ）	—	—	561	［72］
	原子转移自由基聚合	原淀粉/纤维素/丙烯酸	Cu（Ⅱ）	—	—	957	［12］

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