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We report a feasible method to control self‐recognition during the self‐assembly of a hydrophilic macroion, phosphate‐functionalized γ‐cyclodextrin (γ‐CD‐P), though host‐guest interactions. We confirmed that γ‐CD‐P can form a host‐guest complex with a super‐chaotropic anion, namely the B₁₂F₁₂²⁻borate cluster, by using NMR spectroscopy and isothermal titration calorimetry. The loaded γ‐CD‐P, which has a higher charge density, can be distinguished from the uncomplexed γ‐CD‐P, leading to self‐sorting behavior during the self‐assembly process, confirmed by the formation of two types of individual supramolecular structures (R_hof ca. 57 nm and 18 nm, determined by light scattering) instead of hybrid structures in mixed dilute solution. This self‐recognition behavior is accounted for by the difference in intermolecular electrostatic interactions arising from the loading.

 

The solvation shell structures of Ca 2+ in aqueous and organic solutions probed by calcium L-edge soft X-ray absorption spectroscopy (XAS) and DFT/MD simulations show the coordination number of Ca 2+ to be negatively correlated with the electrolyte concentration and the steric hindrance of the solvent molecule. In this work, the calcium L-edge soft XAS demonstrates its sensitivity to the surrounding chemical environment. Additionally, the total electron yield (TEY) mode is surface sensitive because the electron penetration depth is limited to a few nanometers. Thus this study shows its implications for future battery studies, especially for probing the electrolyte/electrode interface for electrochemical reactions under in situ /operando conditions. 

We observe the formation of highly controllable and responsive onion-like vesicles by using rigid sphere−rod amphiphilic hybrid macromolecules, composed of charged, hydrophilic Keggintype clusters (spheres) and hydrophobic rod-like oligofluorenes (OFs). Unlike the commonly used approach, which mainly relies on chain bending of flexible molecules to satisfy different curvatures in onion-like vesicles, the rigid hybrids form flexible interdigitations by tuning the angles between OFs, leading to the formation of bilayers with different sizes. The self-assembled vesicles possess complete onion-like structures from most inner to outer layers, and their size (layer number) can be accurately manipulated by different solution conditions including solvent polarity, ionic strength, temperature, and hybrid concentration, with fixed interbilayer distance under all conditions. Moreover, the vesicle size (layer number) shows excellent reversibility to the change of temperature. The charged feature of spheres, rod length, and overall hybrid architecture shows significant effects on the formation of such onion-like vesicles.