双醛纤维素/聚乙烯醇复合水凝胶的制备及其性能

杨明琰; 陈欣玥; 张笑; 管舒仪; 蔡晓丹; 张文博; 王福俊; 李鑫; 王新平

doi:10.13801/j.cnki.fhclxb.20211018.002

双醛纤维素/聚乙烯醇复合水凝胶的制备及其性能

doi: 10.13801/j.cnki.fhclxb.20211018.002

杨明琰^{1, 2, ,},
陈欣玥¹,
张笑³,
管舒仪¹,
蔡晓丹¹,
张文博¹,
王福俊¹,
李鑫¹,
王新平¹

1.
长安大学　水利与环境学院，西安 710061
2.
旱区地下水文与生态效应教育部重点实验室，西安 710061
3.
陕西省地质矿产实验研究所有限公司，西安 710054

基金项目: 陕西省重点研发计划—社会发展项目(2021SF-443)；长安大学2020年大学生创新创业训练计划专项建设经费和国家级项目的教育部财政资助经费(S202010710510)

详细信息

通讯作者:
杨明琰，博士，副教授，硕士生导师，主要从事木质纤维素资源化利用研究　E-mail: yangmingyan67@163.com

中图分类号: TB332
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出版历程
- 收稿日期: 2021-08-31
- 修回日期: 2021-09-22
- 录用日期: 2021-10-01
- 网络出版日期: 2021-10-19
- 刊出日期: 2022-08-22

Preparation and properties of dialdehyde cellulose/polyvinyl alcohol composite hydrogel

1.
School of Water Conservancy and Environment, Chang′an University, Xi′an 710061, China
2.
Key Laboratory of Underground Hydrology and Ecological Effects in Arid Regions, Xi'an 710061, China
3.
Shaanxi Institute of Geology and Mineral Resources Experiment CO., LTD., Xi'an 710054, China

摘要

摘要: 开发高性能功能性水凝胶并建立药物缓释模型对医用伤口创面材料的开发具有重要的意义。以小麦秸秆为原料通过对甲苯磺酸(p-TsOH)、高频超声、高碘酸盐氧化制备含木质素的生物交联剂双醛纤维素(2,3-dialdehyde cellulose，DAC)；以DAC为交联剂与聚乙烯醇(PVA)通过羟醛缩合反应形成互穿网络结构的DAC/PVA复合水凝胶，研究了DAC含量对复合水凝胶的微观结构、吸水溶胀性能、抗压缩性能及热稳定性的影响；采用物理共混法包埋氨苄青霉素(AP)制备DAC/PVA-AP载药水凝胶并研究其药物释放过程、释放机制及抑菌作用。结果表明，DAC/PVA复合水凝胶的微观结构呈多孔3D网络立体结构，交联密度随DAC含量的增加而增加；复合水凝胶的含水量及溶胀率随着DAC含量的增加而减小，当DAC含量从0.8wt%增加至2.0wt%时，其吸水溶胀率从1823.54%±13.89%降至1105.41%±7.06%；在70%的应变下，1.0wt%DAC/PVA水凝胶的初始抗压强度达到5.765 MPa，抗压缩性能较强；经121℃高温湿热灭菌后，复合水凝胶均能保持完整的形貌，说明其具有优异的耐高温性能；DAC/PVA-AP载药水凝胶的释放模型符合Korsmeyer-Peppas模型，缓释溶液对测试细菌具有良好的抑菌作用。以小麦秸秆为原料制备的互穿网络结构DAC/PVA复合水凝胶具有力学性能好、能耐高温灭菌等优点，在伤口创面敷料等领域具有潜在的应用价值。
- 生物交联剂 /
- 双醛纤维素(DAC) /
- DAC/PVA复合水凝胶 /
- 抗压缩性能 /
- 耐高温性能 /
- 创面敷料
Abstract: Wheat straw was used as raw material to prepare lignin containing 2,3-dialdehyde cellulose (DAC) through sequential treatment of p-toluenesulfonic acid (p-TsOH), ultrasonication, sodium periodate oxidation. DAC was used as crosslinker to prepare 2,3-dialdehyde cellulose/polyvinyl alcohol (DAC/PVA) composite hydrogel through aldol condensation reaction. The microstructures, swelling properties, compression resistance and thermal stability of hydrogels were studied. Ampicillin (AP) was introduced to DAC/PVA composite hydrogel by embedding method to prepare DAC/PVA-AP hydrogel. Drug release process, release mechanism and antibacterial effect were studied as well. The results show that the microstructures of DAC/PVA composite hydrogels show a porous 3D network structure, and the crosslinking density increases with the increase of DAC. The water content and swelling property of composite hydrogel decrease with the increase of DAC. When the DAC concentration increases from 0.8wt% to 2.0wt%, the water absorption swelling rate decreases from 1823.54%±13.89% to 1105.41%±7.06%. The initial compressive strength of 1.0wt%DAC/PVA hydrogel reaches 5.765 MPa under 70% compression strain and present strong compression resistance. After sterilization at 121℃, the composite hydrogels can keep intact morphology, indicating that they have excellent high temperature resistance. The release model of DAC/PVA-AP hydrogel conforms to the Korsmeyer-Peppas model, and the sustained-release solution has a good antibacterial effect on the test bacteria. The DAC/PVA composite hydrogel prepared from wheat straw has a three-dimensional network structure, good mechanical properties and high temperature resistance, and has potential application the field of wound dressings.
- biological crosslinker /
- 2,3-dialdehyde cellulose (DAC) /
- DAC/PVA composite hydrogel /
- compressive resistance property /
- high temperature resistance performance /
- wound dressing

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图 1 DAC/PVA复合水凝胶工艺设计流程

Figure 1. Overview scheme of preparation of DAC/PVA composite hydrogel

p-TsOH—p-toluenesulfonic acid; DAC—2,3-dialdehyde cellulose; PVA—Polyvinyl alcohol

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图 2 纳米纤维素高碘酸钠氧化机制

Figure 2. Sodium periodate oxidation mechanism of nanocellulose

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图 3 LCNFs和DAC的红外光谱(a)及热稳定性结果(b)

Figure 3. Infrared spectra (a) and thermal stability results (b) of LCNFs and DAC

LCNFs—Lignin containing nanofibrils; DTG—Derivative thermogravimetry

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图 4 (a) DAC、PVA交联机制；DAC/PVA复合水凝胶(b)及SEM图像(((c)~(f))分别为0.8wt%、1.0wt%、1.5wt%和2.0wt%DAC/PVA复合水凝胶)

Figure 4. (a) Crosslinking mechanism; DAC/PVA composite hydrogel (b) and SEM images of composite hydrogels (((c)-(f)) are 0.8wt%, 1.0wt%, 1.5wt% and 2.0wt%DAC/PVA composite hydrogels, respectively)

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图 5 DAC/PVA复合水凝胶的抗压缩性能：(a) 70%压缩应变下循环压缩10次的软化率；(b) 1.0wt%DAC/PVA水凝胶在不同应变下经过压缩10次的循环压缩曲线；(c) 1.0wt%DAC/PVA水凝胶在不同应变下经过压缩10次的软化率

Figure 5. Compression resistance of DAC/PVA composite hydrogel: (a) Softening ratio after 10 cycles of compression under 70% compression strain; (b) Cyclic compression curves of 1.0wt%DAC/PVA hydrogel under different strains after 10 times of compression; (c) Softening ratio of 1.0wt%DAC/PVA hydrogel after 10 times compression under different strains

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图 6 DAC/PVA水凝胶高温测试前 (a) 和测试后 (b) 的热稳定性

Figure 6. Thermal stability of DAC/PVA hydrogel before (a) and after (b) high temperature test

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图 7 DAC/PVA水凝胶包埋药物释放曲线(a)及Korsmeryer-Peppas模型线性拟合(b)

Figure 7. Drug release curve of DAC/PVA hydrogel embedding (a) and linear fitting of Korsmeryer-Peppas model (b)

AP—Ampicillin; M_t—Amount of drug released at time t; M_∞—Total drug; t—Sampling time

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图 8 载药复合水凝胶缓释液对E. coli (a)和S. aureus (b)的抑菌圈

Figure 8. Inhibition zone of E. coli (a) and S. aureus (b) by drug loaded compound hydrogel sustained release liquid

a—DAC/PVA-3AP; b—DAC/PVA-6AP; c—DAC/PVA-9AP

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表 1 DAC/PVA复合水凝胶的含水量及溶胀率

Table 1. Water content and swelling rate of DAC/PVA composite hydrogels

Hydrogel sample	Water content/%	Swelling ratio/%
0.8wt%DAC/PVA	82.82±0.04	1823.54±13.89
1.0wt%DAC/PVA	81.21±0.02	1555.16±15.98
1.5wt%DAC/PVA	79.68±0.01	1318.90±14.50
2.0wt%DAC/PVA	79.08±0.01	1105.41±7.06

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表 2 DAC/PVA水凝胶释放AP的Korsmeyer-Peppas模型的主要参数

Table 2. Main parameters of Korsmeyer-Peppas model for AP release by DAC/PVA hydrogel

Type of model	Samples	Fitting parameters
Type of model	Samples	K	n	R²
M_t/M_∞=Ktⁿ	DAC/PVA-3AP	0.17330	0.65996	0.99808
	DAC/PVA-6AP	0.24638	0.57737	0.98744
	DAC/PVA-9AP	0.27144	0.54222	0.99911
Notes: K—Drug release rate; n—Drug release diffusion index; R²—Coefficient of association.

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