Recent advances in analytical techniques for high throughput experimentation.

High throughput experimentation is a growing and evolving field that allows to execute dozens to several thousands of experiments per day with relatively limited resources. Through miniaturization, typically a high degree of automation and the use of digital data tools, many parallel reactions or experiments at a time can be run in such workflows. High throughput experimentation also requires fast analytical techniques capable of generating critically important analytical data in line with the increased rate of experimentation. As traditional techniques usually do not deliver the speed required, some unique approaches are required to enable workflows to function as designed. This review covers the recent developments (2019-2020) in this field and was intended to give a comprehensive overview of the current "state-of-the-art."

Double-Gyroid Nanostructure Formation by Aggregation-Induced Atropisomerization and Co-Assembly of Ionic Liquid-Crystalline Amphiphiles.

We report a new molecular-design principle for creating double-gyroid nanostructured molecular assemblies based on atropisomerization. Ionic amphiphiles containing two imidazolium rings close to each other were designed and synthesized. NMR data revealed that the rotation of the imidazolium rings is restricted, with an activation energy as high as 63 kJ mol-1 in DMSO-d6 solution (DFT prediction for a model compound in the vacuum: 90-100 kJ mol-1 ). Due to the restricted rotation, the amphiphiles feature "double" atropisomeric axes in their ionic segments and form three stable atropisomers: meso, R, and S. These isomers co-organize into I a 3 ‾ d -type bicontinuous cubic liquid-crystalline mesophases through nanosegregation of the ionic and non-ionic parts. Considering the intrinsic characteristic of I a 3 ‾ d -type bicontinuous cubic structures that they are composed of intertwined right- and left-handed single gyroids, we propose that the simultaneous presence of both R- and S-atropisomers is an important contributor to the formation of double-gyroid structures.

Agar-reduced graphene oxide selectively adsorbs organic dyes and strengthens double-network hydrogels.

A straightforward and environmentally friendly method for synthesizing agar-reduced graphene oxide (ArGO) was devised. The topological features and emergent physical properties displayed by the novel carbon material were controlled by varying its water content. Dehydrated films of ArGO were found to be stable in water due to the π-π stacking interactions that formed between the aromatic components of its constituent sheets. In contrast, porous variants of ArGO afforded hydrogels that exhibited high swelling capacities. The intrinsic mechanical strength, elasticity and chemical stability of the hydrogels were further enhanced through adaption into double-network analogues. Such hydrogels, which were prepared using a facile and efficient one-pot methodology, exhibited a high fracture stress upon compression, and retained their shape in basic aqueous environments. These features can be expected to enable water purification and tissue engineering applications, among others.

Covalent bonding of sulfur nanoparticles to unzipped multiwalled carbon nanotubes for high-performance lithium-sulfur batteries.

The use of sulfur as a cathode material for lithium-sulfur (Li-S) batteries has attracted significant attention due to its high theoretical specific capacity (1675 mA h g-1); however, practicality is hindered by a number of obstacles, including the shuttling effect of polysulfides and the low electrical conductivity of sulfur. Herein, ball milling sulfur with unzipped multiwalled carbon nanotubes (UMWNTs) was found to covalently immobilize sulfur nanoparticles to the UMWNTs and resulted in composites (designated as S@UMWNTs) with high electrical conductivity. The unzipping degree of MWNTs was first controlled to optimize the immobilization of sulfur nanoparticles to UMWNTs and the electrochemical performance of the resulting Li-S batteries. The presence of C-S covalent bonds between the UMWNTs and sulfur nanoparticles was verified using x-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy, and the formation of C-S bonds was ascribed to the reactions between the mechanically-induced sulfur radicals and the functional groups of UMWNTs. As a result, when used as a cathode material for Li-S batteries, the S@UMWNTs exhibited excellent electrochemical performance, including a good long-term cycling stability and low capacity decay (e.g., ca. 0.09% per cycle over 500 charge/discharge cycles at 1 C) due to the suppression of the shuttling effect by the C-S covalent bonds.

Dicyanamide Salts that Adopt Smectic, Columnar, or Bicontinuous Cubic Liquid-Crystalline Mesophases.

Although dicyanamide (i.e., [N(CN)2 ]- ) has been commonly used to obtain low-viscosity, halogen-free, room-temperature ionic liquids, liquid-crystalline salts containing such anions have remained virtually unexplored. Here we report a series of amphiphilic dicyanamide salts that, depending on their structures and compositions, adopt smectic, columnar, or bicontinuous cubic thermotropic liquid-crystalline mesophases, even at room temperature in some cases. Their thermal properties were explored by polarized light optical microscopy, differential scanning calorimetry, thermogravimetric analysis (including evolved gas analysis), and variable-temperature synchrotron X-ray diffraction. Comparison of the thermal phase characteristics of these new liquid-crystalline salts featuring "V-shaped" [N(CN)2 ]- anions with those of structural analogues containing [SCN]- , [BF4 ]- , [PF6 ]- , or [CF3 SO3 ]- anions indicated that not only the size of the counterion but also its shape should be considered in the development of mesomorphic salts. Collectively, these discoveries may be expected to facilitate the design of thermotropic ionic liquid crystals that form inverted-type bicontinuous cubic and other sophisticated liquid-crystalline phases.

Lightweight and Ultrastrong Polymer Foams with Unusually Superior Flame Retardancy.

High-performance flame-retardant materials are urgently needed to address outstanding issues that pertain to safety. Traditional flame retardants are toxic to the environment and/or lack the physical properties required for use in many contemporary applications. Here, we show that isocyanate-based polyimide (PI) foam, a flammable material, can exhibit unusually superior flame retardancy as well as other excellent properties, such as being lightweight and displaying high mechanical strength, by incorporating red phosphorus (RP)-hybridized graphene. The covalent bonds formed between the graphene platelets and the PI matrix provide the resultant PI foam with a specific Young's modulus (83 kNm kg-1) that is comparable to or even higher than those displayed by state-of-the-art foams, including silica aerogels, polystyrene foams, and polyurethane foams. In addition, even a low content of the RP-hybridized graphene (2.2 wt %) results in an exceptionally higher limiting oxygen index (39.4) than those of traditional flame-retardant polymer-based materials (typically 20-30). The resultant PI foam also exhibits thermal insulation properties that are similar to that of air. Moreover, the RP-hybridized graphene is prepared using a one-step ball milling process in 100% yield, and does not require solvent or produce waste. The preparation of the flame-retardant PI foams can be scaled as the starting materials are commercially available and the techniques employed are industrially compatible.

Ionic Liquid Crystals: Versatile Materials.

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.

Accurate Diffusion Coefficients of Organosoluble Reference Dyes in Organic Media Measured by Dual-Focus Fluorescence Correlation Spectroscopy.

Dual-focus fluorescence correlation spectroscopy (2fFCS) is a versatile method to determine accurate diffusion coefficients of fluorescent species in an absolute, reference-free manner. Whereas (either classical or dual-focus) FCS has been employed primarily in the life sciences and thus in aqueous environments, it is increasingly being used in materials chemistry, as well. These measurements are often performed in nonaqueous media such as organic solvents. However, the diffusion coefficients of reference dyes in organic solvents are not readily available. For this reason we determined the translational diffusion coefficients of several commercially available organosoluble fluorescent dyes by means of 2fFCS. The selected dyes and organic solvents span the visible spectrum and a broad range of refractive indices, respectively. The diffusion coefficients can be used as absolute reference values for the calibration of experimental FCS setups, allowing quantitative measurements to be performed. We show that reliable information about the hydrodynamic dimensions of the fluorescent species (including noncommercial compounds) within organic media can be extracted from the 2fFCS data.

A causal relation between bioluminescence and oxygen to quantify the cell niche.

Bioluminescence imaging assays have become a widely integrated technique to quantify effectiveness of cell-based therapies by monitoring fate and survival of transplanted cells. To date these assays are still largely qualitative and often erroneous due to the complexity and dynamics of local micro-environments (niches) in which the cells reside. Here, we report, using a combined experimental and computational approach, on oxygen that besides being a critical niche component responsible for cellular energy metabolism and cell-fate commitment, also serves a primary role in regulating bioluminescent light kinetics. We demonstrate the potential of an oxygen dependent Michaelis-Menten relation in quantifying intrinsic bioluminescence intensities by resolving cell-associated oxygen gradients from bioluminescent light that is emitted from three-dimensional (3D) cell-seeded hydrogels. Furthermore, the experimental and computational data indicate a strong causal relation of oxygen concentration with emitted bioluminescence intensities. Altogether our approach demonstrates the importance of oxygen to evolve towards quantitative bioluminescence and holds great potential for future microscale measurement of oxygen tension in an easily accessible manner.

Nematogenic tetracatenar lanthanidomesogens.

We present luminescent liquid-crystalline neodymium(III) complexes that contain three ß-diketonate ligands and a mesogenic 1,10-phenanthroline ligand. Mesomorphism, including a nematic phase--very rare in lanthanide systems--is driven by the highly anisometric phenanthroline.

T-shaped ionic liquid crystals based on the imidazolium motif: exploring substitution of the C-2 imidazolium carbon atom.

In this contribution the first examples of so-called rigid-core, T-shaped imidazolium ionic liquid crystals, in which the C-2 atom of the imidazolium ring is substituted with an aryl moiety decorated with one or two alkoxy chains, are described. The length of the alkoxy chain(s) was varied from six to eighteen carbon atoms (n=6, 10, 14-18). Whereas the compounds with one long alkoxy chain display only smectic A phases, the salts containing two alkoxy chains exhibit smectic A, multicontinuous cubic, as well as hexagonal columnar phases, as evidenced by polarising optical microscopy, differential scanning calorimetry, and powder X-ray diffraction. Structural models are proposed for the self-assembly of the molecules within the mesophases. The imidazolium head groups and the iodide counterions were found to adopt a peculiar orientation in the central part of the columns of the hexagonal columnar phases. The enantiotropic cubic phase shown by the 1,3-dimethyl-2-[3,4-bis(pentadecyloxy)phenyl]imidazolium iodide salt has a multicontinuous Pm ̄3m structure. To the best of our knowledge, this is the first example of a thermotropic cubic mesophase of this symmetry.

1,10-Phenanthrolinium ionic liquid crystals.

The 1,10-phenanthrolinium cation is introduced as a new building block for the design of ionic liquid crystals. 1,10-Phenanthroline, 5-methyl-1,10-phenanthroline, 5-chloro-1,10-phenanthroline, and 4,7-diphenyl-1,10-phenanthroline were quaternized by reaction with 1,3-dibromopropane or 1,2-dibromoethane. The resulting cations were combined with dodecyl sulfate or dioctyl sulfosuccinate anions. The influence of both the cation and anion type on the thermal behavior was investigated. Several of the complexes exhibit mesomorphic behavior, with smectic E phases for the dodecyl sulfate salts and smectic A phases for the dioctyl sulfosuccinate salts. Structural models for the packing of the 1,10-phenanthrolinium and anionic moieties in the liquid-crystalline phases are presented. The ionic compounds show fluorescence in the solid state and in solution.

Polarized luminescence of non-mesogenic europium(III) complexes doped into a nematic liquid crystal.

The luminescence spectra of europium(III) complexes dissolved in the liquid crystal 4'-pentyl-4-cyanobiphenyl (5CB) were investigated. Upon alignment of the europium(III)-doped nematic liquid-crystal host in a liquid-crystal cell with alignment layers, polarization effects were observed in the emission spectra. These polarization effects were visible as differences in the relative intensities of the crystal-field components of the transitions. Although the europium(III) complexes do not need to be liquid-crystalline themselves, some structural anisotropy is required for good alignment in the liquid crystal host and for the generation of linearly polarized light.

Pyrrolidinium ionic liquid crystals with pendant mesogenic groups.

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.

Pyrrolidinium ionic liquid crystals.

N-alkyl-N-methylpyrrolidinium cations have been used for the design of ionic liquid crystals, including a new type of uranium-containing metallomesogen. Pyrrolidinium salts with bromide, bis(trifluoromethylsulfonyl)imide, tetrafluoroborate, hexafluorophosphate, 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 C(n)H(2n+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 uncommon 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 ordered phase. This uncommon tetragonal 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 containing a metal complex anion were investigated. For the uranium-containing mesogens, luminescence can be induced by dissolving them in an ionic liquid matrix. The europium-containing compound shows intense red photoluminescence with high colour purity.