作者:Sivakumar V. Aathimanikandan、Elamprakash N. Savariar、S. Thayumanavan
DOI:10.1021/ja054542y
日期:2005.10.1
Syntheses up to three generations have been achieved of biaryl-based amphiphilic dendrons with a charge-neutral pentaethylene glycol as the hydrophilic part and a decyl chain as the hydrophobic part. Studies on the temperature-dependent characteristics revealed that these dendrons exhibit a generation-dependent lower critical solution temperature (LCST). This behavior is attributed to the combination of the amphipathic nature of the hydrophilic pentaethylene glycol side chain and dendritic effect. Interestingly, this biaryl-based scaffold also maintains the ability to form a micelle-like assembly in polar solvents and an inverted micelle-like assembly in apolar solvents. Polarity of the dendritic interior was investigated using dye-based microenvironment studies. The aggregation behavior of these micelles was analyzed by fluorescence spectroscopy and dynamic light scattering. Critical micelle concentrations (CMC) of these assemblies were investigated using fluorescence excitation spectra of the sequestered guest molecule, pyrene.
Influence of Backbone Conformational Rigidity in Temperature-Sensitive Amphiphilic Supramolecular Assemblies
作者:Krishna R. Raghupathi、Uma Sridhar、Kevin Byrne、Kishore Raghupathi、S. Thayumanavan
DOI:10.1021/jacs.5b02108
日期:2015.4.29
Molecular design, features that, endow amphiphilic supramolecular assemblies with a unique temperature-sensitive transition have been investigated. We find that conformational rigidity in the backbone IS an important feature for eliciting this feature. We also find that intramolecular hydrogen-bonding can in-duce such rigidity in amphiphile backbone. Guest encapsulation stability of these assemblies was found to be significantly altered Within, a narrow temperature window, which correlates with the temperature-sensitive size transition of the molecular assembly. Molecular design principles demonstrated here,could have broad implications in developing future temperature-responsive systems.