A new family of hyperbranched polymeric ionic liquids ("hyperILs") with onion-like topology and facile polarity design were tailored as transporters and compartmentalized systems. Applications include transport and dispersion of water-soluble dyes and functionalized graphene nanosheets from aqueous phase into nonpolar fluids, including polymer melts.

In this manuscript we present a new approach for the fabrication of ZnO nanoparticle based semiconducting thin films. The films are obtained by spin coating of stable nanoparticle dispersions with low boiling point ligands. As the ligands might hinder efficient charge transport between the particles in electronic devices, we present a method to remove them by a vacuum-induced ''sintering'' process of the particles at room temperature. Amine stabilized ZnO nanoparticles were obtained by the decomposition of diethylzinc (Et 2 Zn) in the presence of amines. If butylamine is used as the ligand, NMR and XPS measurements show that complete removal of butylamine can be achieved by storing the nanoparticles in vacuum overnight. Ligand removal leads to electronic interparticle contact as measured with field effect transistors. The ability to process at room temperature makes this approach highly interesting for temperature-sensitive substrates. The potential of our approach for printed electronics is further shown by patterning nanoparticle dispersions via micro-injection moulding in capillaries as a soft lithographic method.

The precise molecular engineering of amphiphilic diblock copolymers as thermoresponsive polymer ionic liquids (PILs) couples polyisobutylene (PIB) and poly(2ethyl-2-oxazoline) (PEtOx) blocks via an imidazolium cation. It enables thermal switching of micellar self-assembly and yields nanostructured hydrogels. Just one ionic liquid (IL)type imidazolium cation is readily incorporated into the backbone of the PIB−IL−PEtOx block copolymers by terminating the cationic 2-ethyl-2-oxazoline (EtOx) ringopening polymerization by alkylation of an imidazoleterminated PIB. The PEtOx block length varies as a function of the PIB-imidazole/EtOx molar ratio and governs solubility, hydrophilic/hydrophobic balance, and nanophase separation. In spite of the presence of highly hydrophobic PIB segments, PIB−IL−PEtOx are rendered water soluble with increasing PEtOx block length and form spherical and elongated micelles as well as hydrogels exhibiting wormlike nanostructures. Furthermore, the lower critical solution temperature of PEtOx segments is the key to thermoresponsive behavior of both water-soluble copolymers and copolymer hydrogels. Owing to low glass temperature and high stability of PIB, these PIB−PILs represent attractive macromolecular nanosystems enabling thermal switching of solubilization, dispersion, transport, and shuttling of molecules and nanoparticles.

Herein we report on a versatile graf ting-to process combined with end group modification to prepare treelike polymeric ionic liquids which are covalently attached to graphene nanosheets. When cationic 3-ethyl-3-hydroxymethyloxetane (EHO) polymerization is initiated in the presence of dispersed hydroxy-functional graphene (FG) nanosheets, chain termination reactions account for highly effective grafting of hyperbranched poly(3-ethyl-3-hydroxymethyloxetane) (PEHO) onto FG. Tosylated PEHO hydroxy end groups are highly reactive alkylating agents for N-alkylimidazoles, thus enabling the incorporation of alkylimidazolium cations with tosylate counteranions as outer shell of the treelike FG-PEHO graft copolymer. In sharp contrast to FG, treelike FG-PEHO containing methylimidazolium tosylates as shell are readily dispersed in water to form stable dispersions without requiring either surfactant addition or high shear mixing. Moreover, these novel carbon/polymer hybrid materials self-assemble on surfaces and form films. In view of the facile tuning of their structures and properties, such treelike graphene polyelectolytes qualify for manifold applications.

To enable the programmable thermoresponsive transport of anions between two phases, multifunctional hyperbranched polymer ionic liquids (hyper-PILs) exhibiting micelle-inspired architectures are tailored as molecular shuttles. These polyelectrolytes consist of a hyperbranched poly(3-ethyl-3-hydroxymethyloxetane) (PEHO) core, an inner polyionic imidazolium (Im + ), and an outer thermoresponsive polyoxazoline (POx) shell, which exhibits lower critical solution temperature (LCST) behavior in aqueous medium. The key step of the hyperPIL synthesis is the efficient chain termination of the cationic ring-opening 2-oxazoline polymerization by the addition of polyfunctional imidazole-terminated PEHO. The resulting covalent attachment of the LCST-POx shell renders hyperPIL polyelectrolytes thermoresponsive. As a function of the polyoxazoline chain length and the oxazoline monomer type, the hyperPIL cloud points (T CP ) vary over a wide temperature range. The inner imidazolium shell enables the immobilization and transport of various anionically charged organic and inorganic payloads via anion exchange. Because of the thermal switching of the hydrophilicity/hydrophobicity balance, hyperPILs function as programmable molecular shuttles for anionic payloads transported back and forth between the phases of ethyl acetate and water. Thus, switchable hyperPILs qualify for manifold potential applications such as catalytic processes with facile recycling of homogeneous catalysts via phase transfer.