Free-Standing Thin Hydrogels: Effects of Composition and pH-Dependent Hydration on Mechanical Properties

Free-Standing Thin Hydrogels: Effects of Composition and pH-Dependent Hydration on Mechanical Properties
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独立式薄水凝胶:成分和 pH 依赖性水合对机械性能的影响

DOI:
10.1021/acsapm.1c00511
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发表时间:
2021
影响因子:
5
通讯作者:
Kharlampieva, Eugenia
Kharlampieva, Eugenia
中科院分区:
化学2区
文献类型:
--
作者:
Dolmat, Maksim;Kozlovskaya, Veronika;Cropek, Donald;Kharlampieva, Eugenia

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我们开发了一种方法,以获得纳米薄膜自由浮动聚(甲基丙烯酸)(PMAA)水凝胶膜通过溶解的牺牲SiO2层。水凝胶膜是通过PMAA/聚(N-乙烯基吡咯烷酮)(PVPON)氢键前体通过自旋辅助(SA)多层组装组装的PMAA化学交联制备的。通过蚀刻厚的牺牲SiO2层,将表面锚定的前体膜和水凝胶从硅模板释放到水溶液中。利用原子力显微镜(AFM)研究了释放方法对释放的(PMAA/PVPON)60和(PMAA)60膜的表面形态、厚度和弹性的影响,并证明这些性质既不受膜释放的影响,也不受随后转移到Si晶片上的影响。我们发现,16小时交联(PMAA)60水凝胶和它们的更溶胀的8小时交联对应物(76%的水化在pH = 5)产生自由浮动膜具有良好的机械完整性和强度。交联16 h的(PMAA)60膜的弹性模量从干燥状态下的1.9 ± 0.1 GPa下降到pH = 5时的77 ± 13 MPa,然后下降到pH = 6.5时的14 ± 3 MPa。我们还表明,将Zr(IV)掺入到两倍薄(PMAA)30水凝胶(约60 nm干厚度)中改善了膜的机械鲁棒性,并允许它们成功地释放和转移到Si晶片上。相比之下,无Zr(PMAA)30由于机械脆性而对释放/转移程序的耐受性较低。Zr(IV)和水凝胶之间的临时配位键可以通过EDTA螯合剂从网络中去除。这里开发的剥离方法是简单的,通用的,适用于各种聚合物薄膜。通过这种方法获得的自由浮动的水凝胶可以用作可转移的平台,以开发芯片实验室系统、纳米复合材料压力传感平台、快速光学生物传感器和用于调节细胞粘附和更有效的细胞片回收的响应平台。
We developed an approach to obtain nanothin free-floating poly(methacrylic acid) (PMAA) hydrogel films through the dissolution of a sacrificial SiO2layer. The hydrogel films were produced by chemical crosslinking of PMAA in PMAA/poly(N-vinylpyrrolidone) (PVPON) hydrogen-bonded precursors assembled through spin-assisted (SA) multilayer assembly. Surface-anchored precursor films and hydrogels were released from silicon templates into an aqueous solution via etching the thick sacrificial SiO2layer from the templates. We studied the impact of the release method on the surface morphology, thickness, and elasticity of the released (PMAA/PVPON)60and (PMAA)60films using atomic force microscopy (AFM) and demonstrated that these properties were affected neither by the film release nor by their following transfer onto Si wafers. We found that 16 h crosslinked (PMAA)60hydrogels and their more swollen 8 h crosslinked counterparts (76% hydration at pH = 5) produced free-floating films with good mechanical integrity and strength. The elastic moduli of a 16 h crosslinked (PMAA)60film decreased from 1.9 ± 0.1 GPa in the dry state to 77 ± 13 MPa at pH = 5 and then to 14 ± 3 MPa at pH = 6.5. We also showed that incorporating Zr(IV) into twice thinner (PMAA)30hydrogels (∼60 nm dry thickness) improved film mechanical robustness and allowed their successful release and transfer onto Si wafers. In contrast, Zr-free (PMAA)30were less tolerant to the release/transfer procedure due to mechanical fragility. The temporary coordination links between Zr(IV) and the hydrogel could be removed from the network by an EDTA chelator. The lift-off approach developed here is simple, versatile, and applicable to a wide range of polymer films. The free-floating hydrogels obtained by this method can be used as transferrable platforms to develop lab-on-a-chip systems, nanocomposite pressure sensing platforms, rapid optical biosensors, and responsive platforms for regulating cell adhesion and more effective cell sheet recoveries.
在相位调制椭圆光度法的一次测量中确定薄膜厚度和折射率。
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