单宁酸-端氨基聚氧化丙烯纳米粒子/琼脂糖复合冷冻凝胶的制备及性能

王立伟; 于雪莹; 韩健美; 何炜

doi:10.13801/j.cnki.fhclxb.20220512.003

单宁酸-端氨基聚氧化丙烯纳米粒子/琼脂糖复合冷冻凝胶的制备及性能

doi: 10.13801/j.cnki.fhclxb.20220512.003

王立伟^{1, 2,},
于雪莹^{1, 2},
韩健美^{1, 2},
何炜^{1, 2, ,}

1.
大连理工大学　精细化工国家重点实验室，大连 116023
2.
大连理工大学　化工学院，大连 116023

基金项目: 国家自然科学基金(31971255)

详细信息

通讯作者:
何炜，博士，教授，博士生导师，研究方向为生物医用材料　E-mail：wlhe@dlut.edu.cn

中图分类号: R318.08；TQ427.2
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出版历程
- 收稿日期: 2022-03-28
- 修回日期: 2022-04-18
- 录用日期: 2022-05-02
- 网络出版日期: 2022-05-13
- 刊出日期: 2023-03-15

Preparation and properties of cryogels composed of agarose and nanoparticles of tannic acid and amino-capped poly(propylene glycol)

WANG Liwei^{1, 2
,},
YU Xueying^{1, 2},
HAN Jianmei^{1, 2},
HE Wei^{1, 2
, ,}

1.
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116023, China
2.
School of Chemical Engineering, Dalian University of Technology, Dalian 116023, China

Funds: National Natural Science Foundation of China (31971255)

摘要

摘要: 为拓展琼脂糖基冷冻凝胶的生物功能，本文秉承便捷环保的理念，将原位制备的植物多酚单宁酸(TA)-端氨基聚氧化丙烯(D400)纳米粒子的分散液与琼脂糖溶液简单共混，采用冷冻凝胶技术成功制备新型复合冷冻凝胶(ATD)，并研究TA-D400纳米粒子形成时间(0 h vs 24 h)对冷冻凝胶(即ATD-0和ATD-24)性能的影响。结果表明：ATD复合冷冻凝胶具有互通的大孔结构和粗糙的孔壁，纳米粒子均匀分散在琼脂糖基质中；冷冻凝胶ATD-0和ATD-24的储能模量分别为1.8 kPa和0.8 kPa，显著高于未复合的琼脂糖凝胶；优异的1, 1-二苯基-2-苦基肼(DPPH)自由基清除效果和铁离子还原/抗氧化能力分析法表征结果共同证实ATD的抗氧化功能。同时，在H₂O₂刺激成纤维细胞的实验中，ATD的抗氧化作用改善了细胞的存活率；此外，细胞黏附实验表明ATD支持成纤维细胞、前成骨细胞和原代皮质神经元等多种细胞的黏附。综上所述，TA-D400纳米粒子的引入实现了对琼脂糖凝胶的双重功能化，此类ATD复合冷冻凝胶有望成为组织工程领域的新型多孔支架材料。
- 琼脂糖 /
- 单宁酸 /
- 端氨基聚醚 /
- 纳米粒子 /
- 冷冻凝胶 /
- 抗氧化 /
- 细胞黏附
Abstract: Here a new type of agarose-based composite cryogel has been developed using a facile and green method. By introducing nanoparticles derived of polyphenol tannic acid (TA) and amine-terminated poly(propylene glycol) (D400) to agarose, the TA-D400 nanoparticles/agarose composite cryogel (ATD) was successfully prepared and the effect of TA-D400 complexation time on the properties of the resulting cryogels was studied. The ATD cryogels prepared by the freezing method have an interconnected macroporous structure, and the nanoparticles are embedded in the agarose matrix. The storage modulus of the composite cryogels ATD-0 and ATD-24 with complexation times of 0 h and 24 h is 1.8 kPa and 0.8 kPa respectively. The introduction of nanoparticles increases the mechanical properties of agarose cryogel. The ATD gels are antioxidative, shown by their excellent 1, 1-diphenyl-2-picrohydrazine (DPPH) free radical scavenging ability and total antioxidant capacity based on the ferric ion reducing/antioxidant power (FRAP) assay result. In vitro cytoprotection experiments show that the ATD gels can protect fibroblasts from H₂O₂-induced oxidative damage. Furthermore, the ATD gels support the adhesion of fibroblasts, pre-osteoblasts, and primary cortical neurons. In summary, by rationally introducing TA-D400 nanoparticles, we have developed a multifunctional cryogel with innate ability for cell adhesion and antioxidation, providing a new option of macroporous materials as potential scaffolds for tissue engineering.
- agarose /
- tannic acid /
- amine-terminated polyether /
- nanoparticles /
- cryogels /
- antioxidation /
- cell adhesion

HTML全文

图 1 单宁酸(TA)-端氨基聚氧化丙烯(D400)纳米粒子/琼脂糖复合冷冻凝胶(ATD)的制备示意图

Figure 1. Schematic of the preparation of tannic acid (TA)-terminal amino polypropylene oxide (D400) nanoparticles/agarose composite cryogel (ATD)

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图 2 (a) 各琼脂糖冻干胶的SEM图像；(b) 经异硫氰酸酯荧光素标记的冷冻凝胶在水中的荧光图片

Figure 2. (a) SEM images of agarose cryogels; (b) Fluorescence images of fluorescein isothiocyanate labeled cryogels in water

A—Plain agarose cryogel; x in ATD-x—Complexation times

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图 3 各冷冻凝胶的FTIR图谱 (a)、热重曲线 (b) 和溶胀率 (c)

Figure 3. FTIR spectra (a), TGA curves (b) and swelling ratio curves (c) of various cryogels

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图 4 各冷冻凝胶的储能模量(G')和损耗模量(G")随频率变化

Figure 4. Storage modulus (G') and loss modulus (G") of various cryogels versus frequency

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图 5 (a) 1,1-二苯基-2-苦基肼(DPPH)自由基溶液与各冷冻凝胶作用后的紫外光谱；(b) 铁离子还原/抗氧化能力分析法(FRAP)测定总抗氧化能力

Figure 5. (a) UV-vis spectra of the 1, 1-diphenyl-2-picryl hydrazine (DPPH) radical solution with various cryogel treatments; (b) Total antioxidant capacity measured by ferric ion reducing/antioxidant power (FRAP)

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图 6 光学照片和细胞存活率量化体现复合冷冻凝胶ATD-0和ATD-24保护细胞应对H₂O₂诱导的损伤能力

Figure 6. Protective effects of cryogels on H₂O₂ induced cell death characterized by phase contrast images and cell viability

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图 7 成纤维细胞、前成骨细胞和原代神经元细胞在冷冻凝胶上的荧光染色图像

Figure 7. Fluorescent images of stained fibroblast, pre-osteoblast and cortical neuron on the cryogels

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