Supplementary information files for "Understanding associative polymer self-assembly with shrinking gate fluorescence correlation spectroscopy"

Supplementary files for article " Understanding associative polymer self-assembly with shrinking gate fluorescence correlation spectroscopy"The self-assembly of polymers is integral to their role in liquid formulations. In this study, we combine a dye whose lifetime is sensitive to the nanoviscosity of its local environment with shrinking gate fluorescence correlation spectroscopy (sgFCS) to study the self-assembly of a model telechelic polymer, hydrophobically modified ethoxylated urethane (HEUR). Fluorescence lifetime measurements show a monotonic increase in average lifetime with increasing HEUR concentration driven by a small fraction of dye (&lt;1%) with long lifetimes strongly bound to HEUR. Despite this small fraction, sgFCS isolates the diffusional dynamics of the bound fraction with no a priori assumptions as to the distribution of lifetimes. Sensitivity is greatly enhanced compared to standard FCS, revealing micellar aggregates forming between 0.2 and 1 wt% followed by formation of a percolated network. This sgFCS approach, which we apply for the first time to polymers in this work, is readily extendable to any dye that changes lifetime on binding.<br><br>© The Authors CC BY 3.0

《利用收缩门荧光关联光谱术理解缔合聚合物自组装过程》一文的补充材料。聚合物自组装是其在液体制剂中发挥功能的核心基础。本研究将一种对所处微环境纳米黏度敏感的荧光染料与收缩门荧光关联光谱术（shrinking gate fluorescence correlation spectroscopy，sgFCS）相结合，用于研究模型遥爪聚合物——疏水改性乙氧基化聚氨酯（hydrophobically modified ethoxylated urethane，HEUR）的自组装过程。荧光寿命测试结果表明，平均荧光寿命随HEUR浓度升高呈单调递增趋势，该现象由占比不足1%的强结合型长寿命染料所主导。尽管该结合态染料占比极低，sgFCS仍可在无需预先假设寿命分布的前提下，精准分离出结合态组分的扩散动力学行为。相较于标准荧光关联光谱（standard FCS），本方法的灵敏度得到显著提升，可观测到0.2 wt%至1 wt%浓度区间内胶束聚集体的形成，以及后续渗滤网络的生成。本研究首次将sgFCS方法应用于聚合物体系，该策略可便捷拓展至任何结合过程中发生寿命变化的荧光染料。<br><br>© 本文作者 知识共享署名3.0（CC BY 3.0）许可协议