Influence of Phosphonium Alkyl Substituents on the Rheological and Thermal Properties of Phosphonium-PAA-Based Supramolecular Polymeric Assemblies

A noncovalent synthetic strategy to supramolecular polymeric assemblies, including network structures, is described by the complexation of various phosphonium monocations and dications with the multianion, poly­(acrylic acid). The alkyl chains surrounding the phosphonium cation were systematically varied from butyl, hexyl, to octyl in order to probe the effect of sterics and ion pairing on the resulting macroscopic properties of the assemblies. The supramolecular assemblies were characterized by TGA, DSC, oscillatory rheometry, steady-state flow rheometry, and SAXS. The rheological and thermal properties, as well as the flow activation energies, are highly dependent on the alkyl chain length. All of the supramolecular assemblies have glass transition temperatures lower than room temperature and range from 8 °C to below −40 °C. Di-ButC10PAA has the shortest alkyl chain length and affords the highest glass transition temperature. Correspondingly, it shows the largest viscosity and storage and loss moduli. For example, its viscosity is 3 orders of magnitude greater than di-OctC10PAA. In creep-recovery experiments, di-ButC10PAA shows the highest percent of strain recovery after the stress is removed, followed by di-HexC10PAA and di-OctC10PAA. The rheological and thermal properties of monoIL-PAA assemblies show similar alkyl chain length dependence, but the magnitude is significantly less because of the lack of cross-linking. A reversibility test of the supramolecular networks demonstrates that the ionic network material can fully reassemble within a short time period after disruption of the network due to heat or shear without sacrificing the mechanical properties

Amino Acid–Nucleotide–Lipids: Effect of Amino Acid on the Self-Assembly Properties

Hybrid amphiphiles composed of a lipid covalently linked to biomolecules are attracting considerable attention, owing to their unique physicochemical and biological properties. Herein, we have synthesized novel amino acid–nucleotide–lipids (ANLs), presenting phenylalanine and thymidine residues and saturated or unsaturated diacyl glycerol lipid moieties to investigate the effect of the specific aminoacid moieties on both aggregation properties and interactions of ANLs with single strand polyA RNA. Physicochemical studies (DLS, cryo-TEM, and small angle X-ray scattering) indicate that phenylanaline amino acids inserted at the 5′ position of the nucleotide-lipids stabilize multilamellar systems, whereas unilamellar vesicles are formed preferentially in the case of nucleotide–lipids (NLs). Both NLs and ANLs exhibit weak interactions with complementary polyA RNA as revealed by isothermal titration calorimetry investigations. The multilamellar vesicles obtained with ANLs could be used as a versatile carrier, suitable for both hydrophobic and hydrophilic therapeutic molecules

Unexpected Bilayer Formation in Langmuir Films of Nucleolipids

Langmuir monolayers have been extensively investigated by various experimental techniques. These studies allowed an in-depth understanding of the molecular conformation in the layer, phase transitions, and the structure of the multilayer. As the monolayer is compressed and the surface pressure is increased beyond a critical value, usually occurring in the minimal closely packed molecular area, the monolayer fractures and/or folds, forming multilayers in a process referred to as collapse. Various mechanisms for monolayer collapse and the resulting reorganization of the film have been proposed, and only a few studies have demonstrated the formation of a bilayer after collapse and with the use of a Ca²⁺ solution. In this work, Langmuir isotherms coupled with imaging ellipsometry and polarization modulation infrared reflection absorption spectroscopy were recorded to investigate the air–water interface properties of Langmuir films of anionic nucleolipids. We report for these new molecules the formation of a quasi-hexagonal packing of bilayer domains at a low compression rate, a singular behavior for lipids at the air–water interface that has not yet been documented