Supramolecular structures of uracil-functionalized PEG with multi-diamidopyridine POSS through complementary hydrogen bonding interactions

Abstract

In this study, we synthesized (i) a multi-diamidopyridine-functionalized polyhedral oligomeric silsesquioxane (MD-POSS) through nucleophilic substitution and click 1,3-cycloaddition reactions and (ii) both mono-and bis-uracil (U)-functionalized poly(ethylene glycol) derivatives (U-PEG and U-PEG-U, respectively) through Michael additions of U to acryloyl-functionalized PEG oligomers. Transmission electron microscopy (TEM) and dynamic light scattering (DLS) revealed that supramolecular structures self-assembled from mixtures of MD-POSS and U-PEG and from MD-POSS and U-PEG-U. Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopy confirmed the presence of multiple hydrogen bonding interactions between the diaminopyridine groups of MD-POSS and the U groups of U-PEG and U-PEG-U. Because of these strong reversible intermolecular multiple hydrogen bonds, the POSS-based polymer-like supramolecular materials exhibited improved thermal properties upon increasing the MD-POSS content.

Thymine- and Adenine-Functionalized Polystyrene Form Self-Assembled Structures through Multiple Complementary Hydrogen Bonds

“…There is much interest in supramolecular structures based on complementary multiple-hydrogen-bond arrays prepared from synthetic polymers presenting nucleotide bases on their side chains [21][22][23][24][25][26][27][28][29][30][31][32][33][34]. The binding forces in systems featuring multiple hydrogen bonds can be tuned, leading to inter-association equilibrium constants (K A ) ranging from several hundred up to more than 10 6 [21][22][23][24][25][26][27][28][29][30][31][32][33][34].…”

Supramolecular Functionalities Influence the Thermal Properties, Interactions and Conductivity Behavior of Poly(ethylene glycol)/LiAsF6 Blends

“…were prepared through Michael additions using previously reported procedures [28]. A solution of PEG acrylate, U and potassium tert-butoxide in DMSO in a flask equipped with a condenser was heated on a hot plate (60 °C) for 48 h. After distillation of the DMSO, the solid residue was dissolved in CH 2 Cl 2 and filtered.…”

“…Figure 1 presents DSC traces of the LiAsF 6 /U-PEG and LiAsF 6 /U-PEG-U polymer electrolytes and the changes in the values of T g at different contents of LiAsF 6 . As mentioned in our previous report [28], acrylate-PEG is a crystalline oligomer having values of T g , T c , and T m of −70 °C, −51 °C, and −5 °C, respectively. Addition of the U groups to the PEG derivative caused U-PEG and U-PEG-U to become amorphous, with their values of T g increasing to −34 and −23 °C, respectively.…”

“…According to the results of a previous study [28], we knew that the properties of polymer/salt mixtures can be changed dramatically as a result of ionic aggregation. Here, we first performed thermal analyses to determine whether the properties of these systems were affected by the addition of the lithium salt.…”

Self-Assembled Structures of Diblock Copolymer/Homopolymer Blends through Multiple Complementary Hydrogen Bonds

“…We have also studied the application of multiple hydrogen bonds in modifying the miscibility behavior and supramolecular structures of several nucleobase-functionalized polymers prepared through free radical polymerization [52][53][54][55][56][57][58][59][60][61][62][63][64][65][66]. We found that the preparation of highly A-or T-functionalized vinylbenzyl monomers can be difficult, due to the polarities of these hetero-nucleobase monomers being significantly different from those of typical commercial monomers (e.g., methacrylate or styrene monomers) [52][53][54].…”