Yes / Ionic liquids (ILs) are key materials for the development of a wide range of emerging technologies. Protic ionic liquids, an important class of ILs, have long been envisioned as promising anhydrous electrolytes for fuel cells. It is well known that in comparison to all other cations, protons exhibit abnormally high conductivity in water. Such superprotonic dynamics was expected in protic ionic conductors as well. However, many years of extensive studies led to the disappointing conclusion that this is not the case and most protic ionic liquids display subionic behavior. Therefore, the relatively low conductivity seems to be the main obstacle for the application of protic ionic liquids in fuel cells. Using dielectric spectroscopy, herein we report the observation of highly decoupled conductivity in a newly synthesized protic ionic conductor. We show that its proton transport is strongly decoupled from the structural relaxation, in terms of both temperature dependence and characteristic rates. This finding offers a fresh look on the charge transport mechanism in PILs and also provides new ideas for design of anhydrous materials with exceptionally high proton conductivity. / National Science Centre within the framework of the Opus project (Grant No. DEC 2011/03/B/ST3/02072). Financial assistance from FNP START. The LDRD Program of ORNL, managed by UT-Battelle, LLC, for the U.S. DOE. Support from the NSF under grant CHE-1213444.

La catalyse, les solvants alternatifs et l'économie d'atome font partie des clés pour le développement de nouvelles stratégies durables de synthèse. Des hétérocycles comme les quinoléines substituées, par réaction de cycloisomérisation catalysée par le cuivre en utilisant les liquides ioniques, et les isoquinoléines carbonylées par réaction de carbonylation oxydante catalysée par le palladium dans le méthanol ont été synthétisées. La formation sélective de 1,3-dihydroisobenzofuranes et/ou 1H-isochromènes a été tentée par réaction de cycloisomérisation catalysée par différent métaux de transition. La synthèse d'hétérocycles à cinq chaînons, par exemple furanes, pyrroles et pyrrolin-4-ones à été mise au point par nouvelle réaction de cycloisomérisation catalysée par de sels de platine ou d'or en utilisant des diols, des amino alcools ou des α-amino-ynones dans le PEG sous activation micro-ondes. Les produits sont récupérés pur après une simple étape de précipitation-filtration. Les α-amino-ynones chiral sont synthétisée à partir de N-protégé carboxyanhydrides des aminoacides (UNCAs). Une réaction de iodocyclisation a été aussi développée pour obtenir de nouvelles structures hétérocycliques. / Catalysis, alternative solvents and atom economy represent key areas for the sustainable development of versatile strategies in organic chemistry. Fused heterocycles, such as substituted quinolines by a cycloisomerization reaction using a recyclable catalytic system copper/ionic liquids and isoquinoline-4-carboxylic esters based on PdI2-catalyzed oxidative carbonylation were prepared. A selective 5-exo-dig or 6-endo-dig cyclization route to obtain 1,3-dihydroisobenzofurans and/or 1H-isochromenes was tested by metal transition cycloisomerization reaction of alkynylbenzyl alcohols in PEG. Five membered ring heterocycles such as furans, pyrroles and pyrrolin-4-ones were successfully obtained by a novel platinum or gold-catalyzed cycloisomerization reaction of diols, aminoalcohols or α-amino-ynones in poly(ethylene glycol) (PEG) under microwave irradiation. The heterocyclic systems were recovered pure after a simple precipitation-filtration work-up. The catalytic systems were studied by using the TEM and XPS techniques. The chiral α-amino-ynone substrates were prepared by an original method starting from N-protected carboxyanhydrides of amino acids (UNCAs). Also unprecedented results are reported in the area of iodocyclization to obtain chiral iodopyrrolin-ones.

Pharmaceutical companies and FDA (Federal Drug Administration) rules rely heavily on crystalline active pharmaceutical ingredients delivered as tablets and powders in the form of neutral compounds, salts and solvates of neutral compounds and salts. About half of all drugs sold in the market are in the form of salts which are held together by ionic bonds along with some other forces. Recently, Ionic liquids (ILs) an interesting class of chemical compounds have offered potential opportunity for exploration as novel drug ionic liquid salts, particularly in the field of transdermal/topical drug delivery. Due to the multifunctional nature of these salts they could allow generation of new pathway to manipulate the transport and deposition behaviour of the drug molecule. It is this modular approach of IL that forms the basis of the research presented here, in which pharmaceutically acceptable compounds are combined with selected drugs with known problems. IL salts were generated by combining at least one drug molecule with FDA approved compounds and were assessed for physicochemical properties, skin deposition and permeation studies. Skin deposition data suggested that these systems exhibit high skin retention, which was found to correlate with the molecular weight. On the other hand, permeation data displayed an inverse relationship between flux values and molecular weight of the permeant. Similar work was extended with ILs with mixed anions containing two drugs. The benzalkonium-sulfacetamide ILs were investigated for synergism and the biological studies data display no synergistic effect. It was also illustrated that in-situ IL based ibuprofen hydrogels systems could be manipulated via IL approach for topical application. These findings suggest the potential applicability of IL based formulations for topical delivery of drugs.