亲水-疏水双网络水凝胶的制备及其黏合性能

张克娜; 周家华; 杜德焰; 倪忠斌; 陈明清; 施冬健

doi:10.14133/j.cnki.1008-9357.20221225001

亲水-疏水双网络水凝胶的制备及其黏合性能

doi: 10.14133/j.cnki.1008-9357.20221225001

江南大学化学与材料工程学院, 江苏无锡 214122

基金项目: 国家自然科学基金(52103165)；江苏省自然科学基金(BK20181349)

详细信息

作者简介:
张克娜（1998—），女，硕士，主要研究方向为生物医用高分子材料。E-mail：6200612025@stu.jiangnan.edu.cn

通讯作者:
施冬健，E-mail：djshi@jiangnan.edu.cn

中图分类号: R318.08
计量
- 文章访问数: 114
- HTML全文浏览量: 43
- PDF下载量: 84
- 被引次数: 0
出版历程
- 收稿日期: 2022-12-25
- 网络出版日期: 2023-03-04
- 刊出日期: 2023-04-01

Preparation and Adhesion Properties of Bio-Hydrogels with Hydrophilic-Hydrophobic Double Networks

School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, Jiangsu, China

摘要

摘要: 选用N-丙烯酰基甘氨酸(ACG)与N-丙烯酰基-L-苯丙氨酸(ACP)为单体，通过自由基共聚，制备由氢键和化学交联双网络构筑的P(ACG_x-ACP_y)水凝胶。通过调节ACG和ACP的组分比，对聚合物分子间作用力与凝胶的综合性能进行调控。分别利用搭接剪切和拉伸测试方法对水凝胶的黏合性能进行测试。结果显示：当水凝胶中n（ACG）∶n（ACP）=1∶1时，其黏合性能最好，对猪皮的最大湿黏合强度可达到80.2 kPa；同时，水凝胶的最高压缩强度最高可达2.2 MPa；细胞毒性试验显示水凝胶的生物相容性良好。
- N-丙烯酰基甘氨酸 /
- N-丙烯酰基-L-苯丙氨酸 /
- 湿黏合 /
- 分子间作用力 /
- 生物相容性
Abstract: Wet (underwater) adhesive materials have wide applications in biomedical and engineering fields. However, a hydration layer on the substrate surface severely prevents the interface interaction between adhesives and substrates, resulting in sharp reduce or even disappearance of the wet adhesion property. Therefore, it is of great significance to prepare adhesive materials with wet adhesion property by removal of the hydration layer via hydrophobic interaction. In this paper, amino acid based monomers, N-acrylylglycine (ACG) and N-acrylyl-L-phenylalanine (ACP) were synthesized, and then poly(N-acrylylglycine-N-acrylyl-L-phenylalanine) hydrogels (P(ACG_x-ACP_y)) were further prepared via hydrogen cross-linking and chemical cross-linking. The intermolecular interactions and properties of the P(ACG_x-ACP_y) hydrogels were regulated by adjusting the composition ratio of ACG to ACP. Their adhesive properties were then detected by lap-shear and tensile tests, respectively. The results showed that the hydrogels had well adhesive properties. The maximum wet lap-shear adhesive strength to pig skin could reach 80.2 kPa, when the molar ratio of ACG to ACP of hydrogel was 1∶1. Moreover, the highest compression strength of the hydrogels was 2.2 MPa. Cytotoxicity tests showed that hydrogels had good biocompatibility. The prepared P(ACG_x-ACP_y) adhesives has the potential applications to bio-tissue and other wet materials repairing.
- N-acrylylglycine /
- N-acrylyl-L-phenylalanine /
- wet adhesion /
- intermolecular interaction /
- biocompatibility

HTML全文

图 1 (a) P(ACG_x-ACP_y)水凝胶的制备过程；P(ACG_x-ACP_y)水凝胶中(b)氢键相互作用和(c)化学交联示意图

Figure 1. (a) Fabrication procedure of P(ACG_x-ACP_y) hydrogels; (b) Hydrogen interaction and (c) chemical crosslink of P(ACG_x-ACP_y) hydrogels

下载: 全尺寸图片幻灯片

图 2 ACP、ACG及P(ACG₁-ACP₁)的FT-IR光谱

Figure 2. FT-IR spectra of ACP, ACG and P(ACG₁-ACP₁)

下载: 全尺寸图片幻灯片

图 3 P(ACG_x-ACP_y)水凝胶的SEM截面形貌

Figure 3. SEM cross-section images of P(ACG_x-ACP_y) hydrogels

下载: 全尺寸图片幻灯片

图 4 P(ACG_x-ACP_y)水凝胶的(a)溶胀曲线和(b)平衡溶胀率

Figure 4. (a) Swelling curves and (b) equilibrium swelling ratios of P(ACG_x-ACP_y) hydrogels

下载: 全尺寸图片幻灯片

图 5 P(ACG_x-ACP_y)水凝胶降解45 d后的(a)体外降解曲线和(b)降解率

Figure 5. (a) In vitro degradation curves and (b) degradation ratio of P(ACG_x-ACP_y) hydrogels after degradation 45 d

下载: 全尺寸图片幻灯片

图 6 P(ACG_x-ACP_y)水凝胶的(a)储能模量和损耗模量随频率变化的动态扫描曲线，(b) 压缩应力-应变曲线和(c)在80%应变下的压缩模量

Figure 6. (a) Frequency-sweep tests, (b) compression stress-strain curves and (c) compression modulus under 80% strain of P(ACG_x-ACP_y) hydrogels

下载: 全尺寸图片幻灯片

图 7 P(ACG_x-ACP_y)水凝胶与猪皮的湿搭接 (a) 剪切黏合强度，(b) 湿拉伸黏合强度，(c) 潮湿环境下与猪皮黏合机理示意图和(d) 湿搭接剪切黏合强度与文献值对比

Figure 7. (a) Wet lap-shear adhesion strength, (b) wet tensile adhesion strength, (c) schematic illustration of adhesion mechanism and (d) comparison of wet lap-shear adhesion strength of P(ACG_x-ACP_y) hydrogels adhered to pig skins with the literature values

下载: 全尺寸图片幻灯片

图 8 (ACG_x-ACP_y)水凝胶(a)在不同基质上的黏附和在(b)湿猪皮、(c)猪心和(d)猪肾上的黏附

Figure 8. Adhesion images of P(ACG_x-ACP_y) hydrogels on (a) different substrates, and on (b) wet pig skin, (c) pig heart, and (d) pig kidney

下载: 全尺寸图片幻灯片

图 9 (a) L929细胞在P(ACG_x-ACP_y)水凝胶浸提液中培养后的细胞活性和(b)培养1 d后的荧光图像

Figure 9. (a) L929 cell viabilities of P(ACG_x-ACP_y) hydrogels after cultured and (b) fluorescence images after cultured of 1 d

下载: 全尺寸图片幻灯片

表 1 P(ACG_x-ACP_y)水凝胶的投料比

Table 1. Feed ratios of P(ACG_x-ACP_y) hydrogels

Sample	n(ACG)/mmol	n(ACP)/mmol	n(ACG)∶n(ACP)	n(NaOH)/mmol
P(ACG₀-ACP₁)	0	1.52	0∶1.52	1.52
P(ACG₁-ACP₂)	0.59	1.18	1∶2	1.77
P(ACG₁-ACP₁)	0.96	0.96	1∶1	1.92
P(ACG₂-ACP₁)	1.40	0.70	2∶1	2.10
P(ACG₁₀-ACP₁)	2.22	0.22	10∶1	2.44
V(H₂O) =1 mL, the monomer mass fraction of each sample is 25%

下载: 导出CSV

参考文献(31)

[1]	ROCHE E T, WOHLFARTH R, OVERVELDE J T B, VASILYEV N V, PIGULA F A, MOONEY D J, BERTOLDI K, WALSH C J. A bioinspired soft actuated material [J]. Advanced Materials,2014,26(8):1200-1206. doi: 10.1002/adma.201304018
[2]	GHOBRIL C, CHAROEN K, RODRIGUEZ E K, NAZARIAN A, GRINSTAFF M W. A dendritic thioester hydrogel based on thiol-thioester exchange as a dissolvable sealant system for wound closure [J]. Angewandte Chemie: International Edition,2013,52(52):14070-14074. doi: 10.1002/anie.201308007
[3]	FEINER R, ENGEL L, FLEISCHER S, MALKI M, GAL I, SHAPIRA A, SHACHAM-DIAMAND Y, DVIR T. Engineered hybrid cardiac patches with multifunctional electronics for online monitoring and regulation of tissue function [J]. Nature Materials,2016,15(6):679-685. doi: 10.1038/nmat4590
[4]	BAE K H, KURISAWA M. Emerging hydrogel designs for controlled protein delivery [J]. Biomaterials Science,2016,4(8):1184-1192. doi: 10.1039/C6BM00330C
[5]	林柏仲, 赵丽, 王宏伟, 朱浩鹏, 盖广清, 王立艳, 丁建勋. 生物黏合水凝胶研究进展 [J]. 功能高分子学报,2020,33(2):125-140. doi: 10.14133/j.cnki.1008-9357.20190711001 LIN B Z, ZHAO L, WANG H W, ZHU H P, GAI G Q, WANG L Y, DING J X. Progress in bioadhesive hydrogels [J]. Journal of Functional Polymers,2020,33(2):125-140. doi: 10.14133/j.cnki.1008-9357.20190711001
[6]	CUI C Y, FAN C C, WU Y H, XIAO M, WU T L, ZHANG D F, CHEN X Y, LIU B, XU Z Y, QU B, LIU W G. Water-triggered hyperbranched polymer universal adhesives: From strong underwater adhesion to rapid sealing hemostasis [J]. Advanced Materials,2019,31(49):1905761. doi: 10.1002/adma.201905761
[7]	LI J, CELIZ A D, YANG J, YANG Q, WAMALA I, WHYTE W, SEO B R, VASILYEV N V, VLASSAK J J, SUO Z, MOONEY D J. Tough adhesives for diverse wet surfaces [J]. Science,2017,357(6349):378-381. doi: 10.1126/science.aah6362
[8]	LI X D, DU Z L, SONG Z Y, LI B, WU L X, LIU Q P, ZHANG H Y, LI W. Bringing hetero-polyacid-based underwater adhesive as printable cathode coating for self-powered electrochromic aqueous batteries [J]. Advanced Functional Materials,2018,28(23):1800599. doi: 10.1002/adfm.201800599
[9]	WANG Y, ZHANG L W, GUO Y R, GAN Y, LIU G, ZHANG D Y, CHEN H W. Air bubble bridge-based bioinspired underwater adhesion [J]. Small,2021,17(42):2103423. doi: 10.1002/smll.202103423
[10]	FAN H L, WANG J H, TAO Z, HUANG J C, RAO P, KUROKAWA T, GONG J P. Adjacent cationic-aromatic sequences yield strong electrostatic adhesion of hydrogels in seawater [J]. Nature Communications,2019,10:5127. doi: 10.1038/s41467-019-13171-9
[11]	XIE C M, WANG X, HE H, DING Y H, LU X. Mussel-inspired hydrogels for self-adhesive bioelectronics [J]. Advanced Functional Materials,2020,30(25):1909954. doi: 10.1002/adfm.201909954
[12]	吴可可, 赵益涛, 吴敏, 李越, 胡志奇, 卢智慧, 郭金山. 聚合物基仿生医用胶黏剂的开发与应用 [J]. 功能高分子学报,2021,34(2):93-113. WU K K, ZHAO Y T, WU M, LI Y, HU Z Q, LU Z H, GUO J S. Development and applications of polymeric biomimetic tissue adhesives [J]. Journal of Functional Polymers,2021,34(2):93-113.
[13]	NORTH M, CHELSEY A, GROSSO D, WILKER J J. High strength underwater bonding with polymer mimics of mussel adhesive proteins [J]. ACS Applied Materials & Interfaces,2017,9(8):7866-7872.
[14]	FAN H L, WANG J H, GONG J P. Barnacle cement proteins-inspired tough hydrogels with robust, long-lasting, and repeatable underwater adhesion [J]. Advanced Functional Materials,2021,31(11):2009334. doi: 10.1002/adfm.202009334
[15]	MEREDITH H J, JENKINS C L, WILKER J J. Enhancing the adhesion of a biomimetic polymer yields performance rivaling commercial glues [J]. Advanced Functional Materials,2014,24(21):3259-3267. doi: 10.1002/adfm.201303536
[16]	YU X, DONG C, ZHUANG W, SHI D J, DONG W F, CHEN M Q, KANEKO D. Bio-based hotmelt adhesives with well-adhesion in water [J]. Polymers,2021,13(4):666. doi: 10.3390/polym13040666
[17]	SU X, XIE W Y, WANG P D, TIAN Z L, WANG H, YUAN Z Y, LIU X Z, HUANG J Y. Strong underwater adhesion of injectable hydrogels triggered by diffusion of small molecules [J]. Materials Horizons,2021(8):2199-2207. doi: 10.1039/D1MH00533B
[18]	SU X, LUO Y, TIAN Z L, YUAN Z Y, HAN Y M, DONG R F, XU L, FENG Y T, LIU X Z, HUANG J Y. Ctenophore-inspired hydrogels for efficient and repeatable underwater specific adhesion to biotic surfaces [J]. Materials Horizons,2020,7(10):2651-2661. doi: 10.1039/D0MH01344G
[19]	WANG H, SU X, CHAI Z H, TIAN Z L, XIE W Y, WANG Y X, WAN Z, DENG M G, YUAN Z Y, HUANG J Y. A hydra tentacle-inspired hydrogel with underwater ultra-stretchability for adhering adipose surfaces [J]. Chemical Engineering Journal,2022,428:131049. doi: 10.1016/j.cej.2021.131049
[20]	CHEN Y J, GUO X, MENSAH A, WANG Q Q, WEI Q F. Nature-inspired hydrogel network for efficient tissue-specific underwater adhesive [J]. ACS Applied Materials & Interfaces,2021,13(50):59761-59771.
[21]	PAN M F, NGUYEN K C T, YANG W S, LIU X, CHEN X Z, MAJOR P W, LE L H, ZENG H B. Soft armour-like layer-protected hydrogels for wet tissue adhesion and biological imaging [J]. Chemical Engineering Journal,2022,434:134418. doi: 10.1016/j.cej.2021.134418
[22]	BAI S M, ZHANG X L, CAI P Q, HUANG X W, HUANG Y Q, LIU R, ZHANG M Y, SONG J B, CHEN X D, YANG H H. A silk-based sealant with tough adhesion for instant hemostasis of bleeding tissues [J]. Nanoscale Horizons,2019,4(6):1333-1341. doi: 10.1039/C9NH00317G
[23]	MENG H, LI Y T, FAUST M, KONST S, LEE B P. Hydrogen peroxide generation and biocompatibility of hydrogel-bound mussel adhesive moiety [J]. Acta Biomaterialia,2015,17:160-169. doi: 10.1016/j.actbio.2015.02.002
[24]	MENG H, LIU Y, LEE B P. Model polymer system for investigating the generation of hydrogen peroxide and its biological responses during the crosslinking of mussel adhesive moiety [J]. Acta Biomaterialia,2017,48:144-156. doi: 10.1016/j.actbio.2016.10.016
[25]	崔春燕, 陈薪羽, 刘博, 武腾玲, 范川川, 刘文广. 一种高强度速黏纳米杂化水凝胶“创可贴” [J]. 高分子学报,2019,50(6):613-622. doi: 10.11777/j.issn1000-3304.2019.18270 CUI C Y, CHEN X Y, LIU B, WU T L, FAN C C, LIU W G. A high strength instant adhesive nano-hybrid hydrogel as first-aid bandage [J]. Acta Polymerica Sinica,2019,50(6):613-622. doi: 10.11777/j.issn1000-3304.2019.18270
[26]	LIU J Y, WANG S X, SHEN Q Q, KONG L M, HUANG G S, WU J R. Tough underwater super-tape composed of semi-interpenetrating polymer networks with a water-repelling liquid surface [J]. ACS Applied Materials & Interfaces,2021,13(1):1535-1544.
[27]	FAN X M, FANG Y, ZHOU W K, YAN L Y, XU Y H, ZHU H, LIU H Q. Mussel foot protein inspired tough tissue-selective underwater adhesive hydrogel [J]. Materials Horizons,2021,8(3):997-1007. doi: 10.1039/D0MH01231A
[28]	GAO F, ZHANG Y Y, LI Y M, XU B, CAO Z Q, LIU W G. Sea cucumber-inspired autolytic hydrogels exhibiting tunable high mechanical performances, repairability, and reusability [J]. ACS Applied Materials & Interfaces,2016,8(14):8956-8966.
[29]	FILIPPOV S, HRUBY M, KONAK C, MACKOVA H, SPIRKOVA M, STEPANEK P. Novel pH-responsive nanoparticles [J]. Langmuir,2008,24(17):9295-9301. doi: 10.1021/la801472x
[30]	HAN L, WANG M H, PRIETO-LOPEZ L O, DENG X, CUI J X. Self-hydrophobization in a dynamic hydrogel for creating nonspecific repeatable underwater adhesion [J]. Advanced Functional Materials,2020,30(7):1907064. doi: 10.1002/adfm.201907064
[31]	XIAO L L, WANG Z L, SUN Y, LI B, WU B H, MA C, PETROVSKII V S, GU X Q, CHEN D, POTEMKIN, II, HERRMANN A, ZHANG H J, LIU K. An artificial phase-transitional underwater bioglue with robust and switchable adhesion performance [J]. Angewandte Chemie: International Edition,2021,60(21):12082-12089. doi: 10.1002/anie.202102158