Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 24, Issue 19, Pages 11848-11855Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/d2cp01286c
Keywords
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Funding
- National Natural Science Foundation of China [21971161]
- Shanghai Pujiang Program [19PJ1403700]
- Shanghai Institutions of Higher Learning [TP2019039]
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This study investigates the thermoresponsive properties of a series of monodispersed dendritic macromolecules. It finds that these macromolecules exhibit sharp phase transitions when suitable structural units are combined. The core, branching density, and peripheral terminals are important factors determining the phase transition temperatures. The dendritic macromolecules can undergo fast exchange between the dehydrated and hydrated states at elevated temperature, and can provide structure-dependent confinement to guest dyes through their multi-valent interactions.
Monodispersed molecules of low molar masses showing thermoresponsiveness are appealing both for mechanism investigation of the thermally-modulated dehydration and aggregation on molecular levels and for designing functional intelligent materials. In the present report, thermoresponsive properties of a homologous series of monodispersed dendritic macromolecules carrying three-, four- or six-fold dendritic oligoethylene glycol (OEG) segments were investigated. These dendritic macromolecules carry either methoxyl or ethoxyl terminals, and have different cores (alcohol, methyl ester or methacryloyl) to exhibit different overall hydrophilicity. They show characteristic thermoresponsive properties with sharp phase transitions when suitable structural units are combined. Three structural factors determine their phase transition temperatures, including the cores, branching density and peripheral terminals. Thermally-induced collapse and aggregation are monitored with temperature-varied NMR spectroscopy at the microscale level and optical microscopy at the macroscale level. At elevated temperature, these dendritic macromolecules undergo fast exchange between the dehydrated and the hydrated states. These dendritic macromolecules afford structure-dependent confinement to guest dyes through their multi-valent interactions.
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