Search

International audience; Small π-conjugated molecules can be designed and synthesized to undergo controlled self-assembly forming low-dimensional architectures, with programmed order at the supramolecular level. Such order is of paramount importance because it defines the property of the obtained material. Here, we have focused our attention to four pyromellitic diimide derivatives exposing different types of side chains. The joint effect of different noncovalent interactions including π–π stacking, H-bonding, and van der Waals forces on the four derivatives yielded different self-assembled architectures. Atomic force microscopy studies, corroborated with infrared and nuclear magnetic resonance spectroscopic measurements, provided complementary multiscale insight into these assemblies.

The hierarchical self-assembly of l-tyrosine substituted naphthalenediimide has been explored in solution by NMR spectroscopy and in the solid-state by atomic force microscopy. Spontaneous non-covalent polymerisation led to the formation of a three-dimensional fibre-like supramolecular polymer with n-type semiconducting properties.

The functionalization of a spherical Keplerate-type polyoxometalate {Mo72V30} with a cationic azobenzene surfactant has been achieved through ionic self-assembly. The photoisomerisation reaction of this complex, which emerges in a light-triggered aggregation–disaggregation process, has been followed by 1H NMR spectroscopy, dynamic light scattering, absorption spectroscopy and scanning electron microscopy analyses.

Polycaprolactone (PCL) and polylactide (PLA) are the two most common biodegradable polymers with potential use in oral applications. Both polymers undergo mainly slow hydrolytic degradation in the human body. However, specific conditions of the oral cavity, like elevated temperature, low pH, and presence of saliva affect the rate of hydrolysis. The study examined the properties of solid samples of PCL and PLA subjected to degradation in phosphate buffered saline (PBS) and artificial saliva (AS) at temperatures of 37 or 42 &deg, C, and pH values 2 or 7.4. A number of tests were performed, including measurement of the degree of swelling, weight loss, molecular weight, differential scanning calorimetry, and thermogravimetry of polymers, as well as hardness and tensile strength. Additionally, topography and stiffness of surfaces using atomic force microscopy are presented. It has been noticed that in the artificial saliva, the processes of polymer degradation occur slightly more slowly, and the effects of temperature and pH are less pronounced. We believe that a layer of porcine gastric mucin from artificial saliva that adsorbed on the surface of polymers may have a key role in the observed differences, this layer resembles protective mucin coating tissues in the oral cavity.

Noncovalent self‐assembly creates an effective route to highly sophisticated supramolecular polymers with tunable properties. However, the outcome of this assembly process is highly dependent on external conditions. In this work, a monomeric naphthalene diimide (NDI), designed to allow solubility in a wide range of solvents, can assemble into three distinct noncovalent supramolecular species depending on solvent composition and temperature. Namely, while the self‐assembly in chlorinated solvents yields relatively short, hydrogen‐bonded nanotubes, the reduction of solvent polarity changes the assembly outcome, yielding π–π stacking polymers, which can further bundle into a more complex aggregate. The obtained polymers differ not only in their global morphology but—more strikingly—also in the thermodynamics and kinetics of their supramolecular self‐assembly, involving isodesmic or two‐stage cooperative assembly with kinetic hysteresis, respectively. Ultimately, three distinct assembly states can be accessed in a single experiment.