A series of copolymers containing 50 mol % acrylic acid (AA) and 50 mol % butyl acrylate (BA) but with differing composition profiles ranging from an AA‐BA diblock copolymer to a linear gradient poly(AA‐grad‐BA) copolymer were synthesized and their pH‐responsive self‐assembly behavior was investigated. While assemblies of the AA‐BA diblock copolymer were kinetically frozen, the gradient‐like compositions underwent reversible changes in size and morphology in response to changes in pH. In particular, a diblock copolymer consisting of two random copolymer segments of equal length (16 mol % and 84 mol % AA content, respectively) formed spherical micelles at pH >5, a mix of spherical and wormlike micelles at pH 5 and vesicles at pH 4. These assemblies were characterized by dynamic light scattering, cryo‐transmission electron microscopy and small angle neutron scattering.
In this work, we demonstrated that the hydrogel obtained from a very simple and single synthetic molecule, N-heptyl-galactonamide was a suitable scaffold for the growth of neuronal cells in 3D. We evidenced by confocal microscopy the presence of the cells into the gel up to a depth of around 200 μm, demonstrating that the latter was permissive to cell growth and enabled a true 3D colonization and organization. It also supported successfully the differentiation of adult human neuronal stem cells (hNSCs) into both glial and neuronal cells and the development of a really dense neurofilament network. So the gel appears to be a good candidate for neural tissue regeneration. In contrast with other molecular gels described for cell culture, the molecule can be obtained at the gram scale by a one-step reaction. The resulting gel is very soft, a quality in accordance with the aim of growing neuronal cells, that requires low modulus substrates similar to the brain. But because of its fragility, specific procedures had to be implemented for its preparation and for cell labeling and confocal microscopy observations. Notably, the implementation of a controlled slow cooling of the gel solution was needed to get a very soft but nevertheless cohesive gel. In these conditions, very wide straight and long micrometric fibers were formed, held together by a second network of flexible narrower nanometric fibers. The two kinds of fibers guided the neurite and glial cell growth in a different way. We also underlined the importance of a tiny difference in the molecular structure on the gel performances: parent molecules, differing by a one-carbon increment in the alkyl chain length, N-hexyl-galactonamide and N-octyl-galactonamide, were not as good as N-heptyl-galactonamide. Their differences were analyzed in terms of gel fibers morphology, mechanical properties, solubility, chain parity, and cell growth.
1 August 2018 in Colloids and Surfaces B: Biointerfaces
In this work, we describe how a simple single low molecular weight gelator (LMWG) molecule – N-heptyl-D-galactonamide, which is easy to produce at the gram scale – is spun into gel filaments by a wet spinning process based on solvent exchange. A solution of the gelator in DMSO is injected into water and the solvent diffusion triggers the supramolecular self-assembly of the N-heptyl-D-galactonamide molecules into nanometric fibers. These fibers entrap around 97% of water, thus forming a highly hydrated hydrogel filament, deposited in a well organized coil and locally aligned. This self-assembly mechanism also leads to a very narrow distribution of the supramolecular fiber width, around 150 nm. In addition, the self-assembled fibers are oriented radially inside the wet-spun filaments and at a high flow rate, fibers are organized in spirals. As a result, this process gives rise to a high control of the gelator self-assembly compared with the usual thermal sol–gel transition. This method also opens the way to the controlled extrusion at room temperature of these very simple, soft, biocompatible but delicate hydrogels. The gelator concentration and the flow rates leading to the formation of the gel filaments have been screened. The filament diameter, its internal morphology, the solvent exchange and the velocity of the jet have been investigated by video image analysis and electron microscopy. The stability of these delicate hydrogel ropes has been studied, revealing a polymorphic transformation into macroscopic crystals with time under some storage conditions. The cell viability of a neuronal cell line on the filaments has also been estimated.
This work deals with the synthesis of a new magnetic liquid crystalline material: a side chain liquid crystal silicone, doped with magnetic cobalt nanorods. This new material presents very promising magnetic properties, discussed in terms of the influence of the lateral liquid crystal groups.
An amphiphilic polymer (CmPOX) based on poly(2-methyl-2-oxazoline) linked to a hydrophobic part composed of an aliphatic chain ending with a photo-active coumarin group has been synthesized. It exhibits the ability of forming small polymeric self-assemblies, typically of ca. 10 nm in size, which were characterized by TEM, cryo-TEM and DLS. The nanocarriers were further formulated to yield photo-crosslinked systems by dimerization of coumarin units of coumarin-functionalized poly(methyl methacrylate) (CmPMMA) and CmPOX. The formed vectors were used to encapsulate Pheophorbide a, a known photosensitizer for photodynamic therapy. Cytotoxicity as well as phototoxicity experiments performed in vitro on human tumor cells revealed the great potential of these nanovectors for photodynamic therapy.