Intermolecular interaction of thermoresponsive poly-2-isopropyl-2-oxazoline in solutions and interpolymer complex with fiber-forming polyethylene oxide

The cross-linked poly-2-isopropyl-2-oxazolines (PiPrOx) differing in cross-linker content have been synthesized and characterized by light scattering, chromatography, and rheometry. The dramatic influence of the cross-linker content on solubility and uni- or bimodality was observed. For the first time, the interpolymer complex of cross-linked PiPrOx with polyethylene oxide is manufactured in fibrous form by the electrospinning method. The role of intermolecular hydrogen bonds in the structure and properties of electrospun fibers (EF) was studied by infrared spectroscopy, differential scanning calorimetry, and scanning electron microscopy. It was established that these interactions allow to obtain a uniform fibrous membrane. At the same time, hydrogen bonding is responsible for the self-organization of PiPrOx in water.     

Intracellular Fate of Hydrophobic Nanocrystal Self‐Assemblies in Tumor Cells

Control of interactions between nanomaterials and cells remains a biomedical challenge. A strategy is proposed to modulate the intralysosomal distribution of nanoparticles through the design of 3D suprastructures built by hydrophilic nanocrystals (NCs) coated with alkyl chains. The intracellular fate of two water‐dispersible architectures of self‐assembled hydrophobic magnetic NCs: hollow deformable shells (colloidosomes) or solid fcc particles (supraballs) is compared. These two self‐assemblies display increased cellular uptake by tumor cells compared to dispersions of the water‐soluble NC building blocks. Moreover, the self‐assembly structures increase the NCs density in lysosomes and close to the lysosome membrane. Importantly, the structural organization of NCs in colloidosomes and supraballs are maintained in lysosomes up to 8 days after internalization, whereas initially dispersed hydrophilic NCs are randomly aggregated. Supraballs and colloidosomes are differently sensed by cells due to their different architectures and mechanical properties. Flexible and soft colloidosomes deform and spread along the biological membranes. In contrast, the more rigid supraballs remain spherical. By subjecting the internalized suprastructures to a magnetic field, they both align and form long chains. Overall, it is highlighted that the mechanical and topological properties of the self‐assemblies direct their intracellular fate allowing the control intralysosomal density, ordering, and localization of NCs.     

Photonic Crystals from Ordered Mesoporous Thin‐Film Functional Building Blocks

Environment‐sensitive Bragg reflectors are built using functional mesoporous thin films as building blocks. Tuning of optical properties is achieved by changing the composition or porosity of the slabs or the introduction of planar defects. Sorption or capillary condensation of molecules into the pore system results in a 10–40 nm photonic bandgap (PBG) shift. Organic functions added to the pore surface change the response, permitting tailoring of the selectivity towards small‐size molecules.     

Supramolecular Systems Based on Novel Amphiphiles and a Polymer: Aggregation and Selective Solubilization

Supramolecular systems based on novel triazole-containing and pyrimidine-containing amphiphiles bearing OH-groups and a hydrophilic polymer (polyethyleneimine, PEI) were fabricated. Aggregation threshold of individual amphiphile solutions and a surfactant/polymer binary mixture were determined to be equal to 2 and 0.05 mM, respectively, using tensiometry and conductometry techniques. It was found, that PEI addition to surfactant aqueous solutions induces the transition from open to closed association mode accompanying the decrease of mean hydrodynamic diameter of particles (D _H) from 100 nm to D _H ≤ 5 nm. Polymer addition to the system results in the leveling of pH decrease with surfactant concentration and increase of the electrokinetic potential values from 10 mV up to 40 mV. It was established that solubilization capacity of the supramolecular system formed could be increased by transition from surfactant individual solutions to the amphiphile/polymer binary system. The solubilization properties of the system strongly depend on the nature of the hydrophobic guest solubilized and differ by two orders of magnitude for hydrophobic azodye and lipophilic oxime.     

Porous Supramolecularly Templated Optical Resonators Built in 1D Photonic Crystals

A synthetic route to attain photonic multilayers that presents controlled porosity only at the middle‐layer level is shown. The spectral resonance associated with this porous layer shows strong sensitivity to the presence of vapors adsorbed or condensed within the void network, providing a potentially relevant material for gas detection. The importance of the interplay between pore and probe‐molecule diameters is studied and its implications in size‐selective detection are discussed.