Ionic liquids are remarkable chemical compounds, which find applications in many areas of modern science. Because of their highly tunable nature and exceptional properties, ionic liquids have become essential players in the fields of synthesis and catalysis, extraction, electrochemistry, analytics, biotechnology, etc. Apart from physical and chemical features of ionic liquids, their high biological activity has been attracting significant attention from biochemists, ecologists, and medical scientists. This Review is dedicated to biological activities of ionic liquids, with a special emphasis on their potential employment in pharmaceutics and medicine. The accumulated data on the biological activity of ionic liquids, including their antimicrobial and cytotoxic properties, are discussed in view of possible applications in drug synthesis and drug delivery systems. Dedicated attention is given to a novel active pharmaceutical ingredient-ionic liquid (API-IL) concept, which suggests using traditional drugs in ...

Biological Activity of Ionic Liquids and Their Application in Pharmaceutics and Medicine.

Cooperativity in Noncovalent Interactions.

Light-driven phenomena both in living systems and nonliving materials have enabled truly fascinating and incredible dynamic architectures with terrific forms and functions. Recently, liquid crystalline materials endowed with photoresponsive capability have emerged as enticing systems. In this Review, we focus on the developments of light-driven liquid crystalline materials containing photochromic components over the past decade. Design and synthesis of photochromic liquid crystals (LCs), photoinduced phase transitions in LC, and photoalignment and photoorientation of LCs have been covered. Photomodulation of pitch, polarization, lattice constant and handedness inversion of chiral LCs is discussed. Light-driven phenomena and properties of liquid crystalline polymers, elastomers, and networks have also been analyzed. The applications of photoinduced phase transitions, photoalignment, photomodulation of chiral LCs, and photomobile polymers have been highlighted wherever appropriate. The combination of photoc...

Light-Driven Liquid Crystalline Materials: From Photo-Induced Phase Transitions and Property Modulations to Applications.

This Review covers the recent developments (2005-2015) in the design, synthesis, characterization, and application of thermotropic ionic liquid crystals. It was designed to give a comprehensive overview of the "state-of-the-art" in the field. The discussion is focused on low molar mass and dendrimeric thermotropic ionic mesogens, as well as selected metal-containing compounds (metallomesogens), but some references to polymeric and/or lyotropic ionic liquid crystals and particularly to ionic liquids will also be provided. Although zwitterionic and mesoionic mesogens are also treated to some extent, emphasis will be directed toward liquid-crystalline materials consisting of organic cations and organic/inorganic anions that are not covalently bound but interact via electrostatic and other noncovalent interactions.

Ionic Liquid Crystals: Versatile Materials.

There is no doubt that ionic liquids have become a major subject of study for modern chemistry. We have become used to ever more publications in the field each year, although there is some evidence that this is beginning to plateau at approximately 3500 papers each year. They have been the subject of several major reviews and books, dealing with different applications and aspects of their behaviours. In this article, I will show a little of how interest in ionic liquids grew and developed.

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Ionic liquids: a brief history

N-Alkyl-N-methylpyrrolidini- um cations have been used for the design of ionic liquid crystals, including a new type of uranium-containing me- A Pyrrolidinium salts with bromide, bis(trifluoromethylsulfonyl)- A tetrafluoroborate, hexafluoro- phosphate, thiocyanate, tetrakis(2- thenoyltrifluoroacetonato)europate(III) and tetrabromouranyl counteranions were prepared. For the bromide salts and tetrabromouranyl compounds, the chain length of the alkyl group CnH2n + 1 was varied from eight to twenty carbon atoms (n = 8, 10-20). The compounds show rich mesomorphic behaviour: highly ordered smectic phases (the crystal smectic E phase and the uncom- mon crystal smectic T phase), smectic A phases, and hexagonal columnar phases were observed, depending on chain length and anion. This work gives better insight into the nature and formation of the crystal smectic T phase, and the molecular requirements for the appearance of this highly or- dered phase. This uncommon tetrago- nal mesophase is thoroughly discussed on the basis of detailed powder X-ray diffraction experiments and in relation to the existing literature. Structural models are proposed for self-assembly of the molecules within the smectic layers. In addition, the photophysical properties of the compounds contain- ing a metal complex anion were inves- tigated. For the uranium-containing mesogens, luminescence can be in- duced by dissolving them in an ionic liquid matrix. The europium-containing compound shows intense red photolu- minescence with high colour purity.

Pyrrolidinium ionic liquid crystals.

Piperidinium, piperazinium and morpholinium cations have been used for the design of ionic liquid crystals These cations were combined with several types of anions, namely bromide, tetrafluoroborate, hexafluorophosphate, dodecylsulfate, bis(trifluoromethylsulfonyl)imide, dioctylsulfosuccinate, dicyclohexylsulfosuccinate, and dihexylsulfosuccinate For the bromide salts of piperidinium containing one alkyl chain, the chain length was varied, ranging from 8 to 18 carbon atoms (n = 8, 10, 12, 14, 16, 18) The compounds show a rich mesomorphic behavior High-ordered smectic phases (crystal smectic E and T phases), smectic A phases, and hexagonal columnar phases were observed, depending on the type of cation and anion The morpholinium compounds with sulfosuccinate anions showed hexagonal columnar phases at room temperature and a structural model for the self-assembly of these morpholinium compounds into hexagonal columnar phases is proposed

Piperidinium, piperazinium and morpholinium ionic liquid crystals.

The structures of the self-assembled monolayers of various 4-alkoxybenzoic acids physisorbed at the liquid-solid interface were established by employing scanning tunnelling microscopy (STM). This study has been essentially undertaken to explore the competitive influence of van der Waals and hydrogen-bonding interactions on the process of two-dimensional self-assembly. These acid derivatives form hydrogen-bonded dimers as expected; however, the dimers organise themselves in the form of relatively complex lamellae. The characteristic feature of these lamellae is the presence of regular discommensurations or kinks along the lamella propagation direction. The formation of kinked lamellae is discussed in light of the registry mechanism of the alkyl chains with the underlying graphite substrate. The location of the kinks along a lamella depends on the number (odd or even) of carbon atoms in the alkyl chain. This result indicates that concerted van der Waals interactions of the alkyl chain units introduce the odd/even chain-length effect on the surface-assembled supramolecular patterns. The odd/even effects are retained even upon complexation with a hydrogen-bond acceptor. However, as the solvent is changed from 1-phenyloctane to 1-octanoic acid, the kinked lamellae as well as the odd/even effects disappear. This solvent-induced convergence of supramolecular patterns is attained by means of co-crystallisation of octanoic acid molecules in the 2D crystal lattice, which is evident from high-resolution STM images. The solvent co-adsorption phenomenon is discussed in terms of competing van der Waals and hydrogen-bonding interactions.

Hydrogen Bonding Versus van der Waals Interactions: Competitive Influence of Noncovalent Interactions on 2D Self-Assembly at the Liquid–Solid Interface

New ionic liquid crystals (including ionic metallomesogens) based on the pyrrolidinium core are presented. N-Methylpyrrolidine was quaternized with different mesogenic groups connected to a flexible, omega-bromosubstituted alkyl spacer. The length of the flexible alkyl spacer between the cationic head group and the rigid mesogenic group was varied. The substituted pyrrolidinium cations were combined with bromide, bis(trifluoromethylsulfonyl)imide, tetrakis(2-thenoyltrifluoroacetonato)europate(III), and tetrabromouranyl anions. The influence of the type of mesogenic unit, the lengths of the flexible spacer and terminal alkyl chain, the size of the mesogenic group, and the type of anion on the thermotropic mesomorphic behavior was investigated. Furthermore, the phase behavior was thoroughly compared with the previously reported mesomorphism of N-alkyl-N-methylpyrrolidinium salts. Low-ordered smectic A phases of the de Vries type, smectic C phases, higher-ordered smectic F/I phases, as well as crystal smectic phases (E and G, J, H, or K) were observed and investigated by polarizing optical microscopy, differential scanning calorimetry, and powder X-ray diffraction.

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Kathleen Lava

Papers

Ionic Liquid Crystals: Versatile Materials.

Pyrrolidinium ionic liquid crystals.

Piperidinium, piperazinium and morpholinium ionic liquid crystals.

Hydrogen Bonding Versus van der Waals Interactions: Competitive Influence of Noncovalent Interactions on 2D Self-Assembly at the Liquid–Solid Interface

Pyrrolidinium Ionic Liquid Crystals with Pendant Mesogenic Groups