Priority Research Centre for Advanced Fluids and Interfaces, Newcastle Institute for Energy and Resources, The University of Newcastle, Callaghan, NSW 2308, Australia.
Priority Research Centre for Advanced Fluids and Interfaces, Newcastle Institute for Energy and Resources, The University of Newcastle, Callaghan, NSW 2308, Australia.
J Colloid Interface Sci. 2017 Nov 15;506:486-492. doi: 10.1016/j.jcis.2017.07.068. Epub 2017 Jul 19.
The conformation of poly(ethylene oxide) (PEO) in deep eutectic solvents (DESs) is determined by the polymer-solvent interactions, especially hydrogen bonding interactions. The hypothesis for this work is that the hydrogen bonding environment of a DES can be varied via changing the cation or hydrogen bond donor (HBD), and therefore the solvent quality for PEO; the anion species will also effect hydrogen bonding, but this is not examined here.
Small angle neutron scattering (SANS) is used to probe the concentration dependent conformation of 36kDa PEO dissolved in DESs formed by mixing ethyl or butyl ammonium bromide with a molecular HBD (glycerol or ethylene glycol) in a 1:2 molar ratio.
The radius of gyration (R), Flory exponent and crossover concentration (c) from the dilute to the semi-dilute regime of PEO in the DESs revealed by SANS and Zimm plot analysis show that these DESs are moderately good solvents for PEO. When the ammonium alkyl chain length is increased, the hydrogen bond density per unit volume decreases, and with it the solvent quality for PEO. The solvent quality is improved when the HBD is changed from glycerol to ethylene glycol due to differences in the hydrogen bonding environment for PEO.
聚环氧乙烷(PEO)在深共熔溶剂(DESs)中的构象由聚合物-溶剂相互作用决定,特别是氢键相互作用。这项工作的假设是,通过改变阳离子或氢键供体(HBD),可以改变 DES 的氢键环境,从而改变 PEO 的溶剂质量;阴离子种类也会影响氢键,但这里不进行考察。
小角中子散射(SANS)用于探测在 DESs 中溶解的 36kDa PEO 的浓度依赖性构象,DESs 是由摩尔比为 1:2 的乙基或丁基溴化铵与分子 HBD(甘油或乙二醇)混合形成的。
通过 SANS 和 Zimm 图分析揭示,PEO 在 DESs 中的旋转半径(R)、Flory 指数和从稀到半稀转变的浓度(c)表明,这些 DESs 是 PEO 的中等良好溶剂。当铵烷基链长度增加时,单位体积内的氢键密度降低,PEO 的溶剂质量也随之降低。当 HBD 从甘油变为乙二醇时,由于 PEO 的氢键环境的差异,溶剂质量得到改善。