Fujian Provincial Key Laboratory of Polymer Materials, College of Chemistry and Materials Science, Fujian Normal University, Fujian 350007, China.
Mater Horiz. 2021 Mar 1;8(3):997-1007. doi: 10.1039/d0mh01231a. Epub 2021 Jan 4.
Mussel foot proteins (Mfps) show strong adhesion to underwater substrates, making mussels tightly cling to reefs to withstand the sea current. Therefore, Mfps-inspired tissue adhesives have aroused much research interest, but tough underwater biological tissue adhesion is still a great challenge. Herein, we report a tough and reversible wet tissue-selective adhesive hydrogel made of poly(acrylic acid-co-catechol) and chitosan (CS). It provides negatively charged -COO, positively charged -NH, catechol group and hydrophobic alkyl chain, resemble amino acids, catechol and hydrophobic units in Mfps. Due to the covalent/electrostatic attraction/π-π/cationic-π/hydrogen bonding, in addition to the hydrophobic interaction from the long hydrophobic alkyl chain of the catechol derivative, the hydrogel has a high cohesion strength and toughness, i.e., tensile stress, fracture strain and fracture toughness of ∼0.57 MPa, 2510% and 6620 J m, respectively. As a tissue adhesive, its adhesion bonding to the porcine skin surface is so strong that its adhesion strength is almost equal to the tearing strength of the hydrogel. The 180-degree peeling adhesion energy of the hydrogel to blood-wetted porcine skin is notably ∼1010 J m. It can tightly and seamlessly adhere to the porcine small intestine, and has a bursting pressure of up to 520 mmHg. The hydrogel can be handily debonded from the porcine skin surface in the presence of aqueous solution at pH 8.0, and its adhesiveness is reversible for at least 20 cycles. It is supposed that the synergistic interactions of the adhesive catechol group, displacement of water on the wet skin surface by the positively charged -NH groups of CS and the water-repelling potential of the hydrophobic unit of the catechol derivative, the protection of the catechol group from oxidation into a less adhesive quinone group, and the energy dissipation capacity of the mechanically tough hydrogel contribute to the strong and repeatable wet tissue adhesion.
贻贝足部蛋白(Mfps)对水下基质具有很强的粘附性,使贻贝紧紧地附着在礁石上,以抵御海流。因此,受 Mfps 启发的组织胶粘剂引起了广泛的研究兴趣,但坚韧的水下生物组织粘附仍然是一个巨大的挑战。在此,我们报告了一种由聚(丙烯酸-co-儿茶酚)和壳聚糖(CS)制成的坚韧且可重复使用的湿组织选择性粘附水凝胶。它提供了带负电荷的-COO、带正电荷的-NH、儿茶酚基团和疏水性烷基链,类似于 Mfps 中的氨基酸、儿茶酚和疏水性单元。由于共价/静电吸引/π-π/阳离子-π/氢键,以及儿茶酚衍生物的长疏水性烷基链的疏水相互作用,水凝胶具有高内聚强度和韧性,即拉伸应力、断裂应变和断裂韧性分别约为 0.57 MPa、2510%和 6620 J m。作为一种组织胶粘剂,它对猪皮表面的粘合强度非常高,以至于其粘合强度几乎等于水凝胶的撕裂强度。水凝胶对血湿猪皮的 180 度剥离粘附能显著约为 1010 J m。它可以紧密无缝地粘附在猪小肠上,爆破压力高达 520 mmHg。在 pH 8.0 的水溶液存在下,水凝胶可以方便地从猪皮表面解键合,其粘附性可重复至少 20 次。据推测,协同作用的粘性儿茶酚基团、CS 的带正电荷的-NH 基团在湿皮表面置换水以及儿茶酚衍生物的疏水性单元的疏水性、儿茶酚基团免受氧化成粘性较小的醌基团以及机械坚韧水凝胶的能量耗散能力有助于实现强大且可重复的湿组织粘附。
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