Using Liquid Crystals to Probe the Organization of Helical Polypeptide Brushes Induced by Solvent Pretreatment

Using Liquid Crystals to Probe the Organization of Helical Polypeptide Brushes Induced by Solvent Pretreatment
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利用液晶探测溶剂预处理诱导的螺旋多肽刷的组织

DOI:
10.1021/acs.macromol.1c01125
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发表时间:
2021
期刊:
影响因子:
5.5
通讯作者:
Abbott, Nicholas L.
Abbott, Nicholas L.
中科院分区:
化学1区
文献类型:
--
作者:
Tsuei, Michael;Tran, Hai;Roh, Sangchul;Ober, Christopher K.;Abbott, Nicholas L.

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接枝聚合物刷形成了多功能表面的基础,这些表面可以通过选择接枝聚合物的化学官能团或结构来定制。在这里,我们探索了溶剂处理如何对含有螺旋聚(γ-苄基-l-谷氨酸)(PBLG)的均聚刷的组织进行编程,以及与刷接触的液晶(lc)的取向行为如何为刷的组织提供新的见解。我们用好溶剂(氯仿)或差溶剂(丙酮)处理PBLG刷,分别形成折叠或帐篷状接枝聚合物组织。当支撑在厚度为50 nm的PBLG刷上时,我们发现塌陷和圆锥形刷分别诱导了向列lc的平面(平行于表面)和同向同性(垂直于表面)取向。通过制备不同厚度(12-140 nm)的溶剂预处理电刷,并结合基于原子力显微镜、傅里叶变换红外光谱和液相色谱的见解,我们发现液相色谱的连续倾斜变化伴随着PBLG链的连续倾斜变化,这是受锥形组织的影响。PBLG链取向决定LC取向的作用通过PBLG刷的热变性实验得到证实。最后,当使用混合溶剂(氯仿和丙酮的混合物)来处理PBLG刷组织时,我们观察到lc在微米尺度上呈现出图案取向,与混合溶剂干燥过程中形成的液滴印迹的PBLG链的图案取向一致。总的来说,这些结果扩大了我们对溶剂预处理诱导的PBLG刷组织范围的理解,并证明了lc在刷内成像PBLG链取向的实用性。
Grafted polymer brushes form the basis of a versatile class of surfaces with properties that can be tailored via choice of the chemical functional groups or architecture of the grafted polymers. Here, we explore how treatment by solvents can program the organization of homopolymer brushes comprising helical poly(γ-benzyl-l-glutamate) (PBLG) and how the orientational behavior of liquid crystals (LCs) contacted with the brushes can provide fresh insights into brush organization. We treated PBLG brushes with either good (chloroform) or poor (acetone) solvents to form collapsed or teepee-like grafted polymer organizations, respectively. When supported on PBLG brushes with thicknesses [determined by atomic force microscopy (AFM)] of 50 nm, we found that collapsed and teepee-like brushes induced planar (parallel to surface) and homeotropic (perpendicular to surface) orientations of nematic LCs, respectively. By preparing solvent-pretreated brushes with a range of thicknesses (12–140 nm), and by combining insights based on AFM, Fourier-transform infrared spectroscopy and LCs, we found that a continuous change in tilt of the LC is accompanied by a continuous change in tilt of the PBLG chains, as influenced by the teepee-like organization. The role of PBLG chain orientation in dictating the LC orientation was confirmed by additional experiments in which PBLG brushes were thermally denatured. Finally, when using mixed solvents (mixtures of chloroform and acetone) to manipulate the PBLG brush organization, we observed LCs to exhibit patterned orientations on the micrometer scale, consistent with patterned orientations of the PBLG chains imprinted by droplets formed during the mixed solvent drying process. Overall, these results expand our understanding of the range of PBLG brush organizations that can be induced by solvent pretreatment and demonstrate the utility of LCs for imaging PBLG chain orientation within brushes.
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期刊: Langmuir : the ACS journal of surfaces and colloids
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DOI: --
发表时间: 1977
期刊:
影响因子: --
作者:
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DOI: --
发表时间: 1978
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影响因子: --
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