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Precision Doping of Polyelectrolyte Complexes: Insight on the Role of Ions
Macromolecules ( IF 5.1 ) Pub Date : 2020-06-23 , DOI: 10.1021/acs.macromol.0c00965 Mo Yang 1 , Zachary A. Digby 1 , Joseph B. Schlenoff 1
Macromolecules ( IF 5.1 ) Pub Date : 2020-06-23 , DOI: 10.1021/acs.macromol.0c00965 Mo Yang 1 , Zachary A. Digby 1 , Joseph B. Schlenoff 1
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The properties of polyelectrolyte complexes and coacervates, both termed PECs, are influenced strongly by their ion and water content. Water plasticizes PECs, reducing their modulus and glass transition temperature, Tg. In this work, a hydrated PEC with a Tg near room temperature, made from poly(diallyldimethylammonium) (PDADMA) and poly(styrene sulfonate) (PSS) was precisely doped with 22Na-labeled sodium salts along a Hofmeister series. A distinctive change in the rate of doping versus added salt concentration was observed for all salts. This transition was interpreted to reflect a change in ion-accessible volume coinciding with a change in the role of added salt from counterions for the polyelectrolytes, paired directly and within one water molecule of the charge on the polymer backbone, to a mix of counterions and co-ions, which do not have a specific location within the PEC. Isothermal calorimetry for PEC made in, and doped by, NaCl showed two clear regions for enthalpy change, ΔH, before and after the doping transition. The higher ΔH region was correlated with the counterion role, an indirect measure of the location of ions within the PEC.
中文翻译：
聚电解质配合物的精确掺杂：离子作用的见解
聚电解质复合物和凝聚层的性能（均称为PEC）受其离子和水含量的强烈影响。水使PEC增塑，降低其模量和玻璃化转变温度T g。在这项工作中，水合PEC与Ť克接近室温，由聚（二烯丙基二甲基）制成（PDADMA）和聚（苯乙烯磺酸盐）（PSS）被精确地掺杂有22沿Hofmeister系列的Na标记钠盐。对于所有盐，观察到掺杂速率相对于添加的盐浓度的显着变化。该转变被解释为反映了离子可及体积的变化，这与添加盐的作用发生了变化，从反离子对聚电解质的作用直接发生变化，并直接在聚合物主链上的电荷的一个水分子内配对成反离子和离子在PEC中没有特定位置。用NaCl制成并掺杂的PEC的等温量热法显示出在掺杂转变前后，焓变的两个清晰区域ΔH。较高的ΔH区与抗衡离子作用相关，抗衡离子是PEC中离子位置的间接度量。
更新日期：2020-07-14
中文翻译：
聚电解质配合物的精确掺杂：离子作用的见解
聚电解质复合物和凝聚层的性能（均称为PEC）受其离子和水含量的强烈影响。水使PEC增塑，降低其模量和玻璃化转变温度T g。在这项工作中，水合PEC与Ť克接近室温，由聚（二烯丙基二甲基）制成（PDADMA）和聚（苯乙烯磺酸盐）（PSS）被精确地掺杂有22沿Hofmeister系列的Na标记钠盐。对于所有盐，观察到掺杂速率相对于添加的盐浓度的显着变化。该转变被解释为反映了离子可及体积的变化，这与添加盐的作用发生了变化，从反离子对聚电解质的作用直接发生变化，并直接在聚合物主链上的电荷的一个水分子内配对成反离子和离子在PEC中没有特定位置。用NaCl制成并掺杂的PEC的等温量热法显示出在掺杂转变前后，焓变的两个清晰区域ΔH。较高的ΔH区与抗衡离子作用相关，抗衡离子是PEC中离子位置的间接度量。
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