The nanostructure of a series of choline chloride/urea/water deep eutectic solvent mixtures was characterized across a wide hydration range by neutron total scattering and empirical potential structure refinement (EPSR). As the structure is significantly altered, even at low hydration levels, reporting the DES water content is important. However, the DES nanostructure is retained to a remarkably high level of water (ca. 42 wt % H2O) because of solvophobic sequestration of water into nanostructured domains around cholinium cations. At 51 wt %/83 mol % H2O, this segregation becomes unfavorable, and the DES structure is disrupted; instead, water–water and DES–water interactions dominate. At and above this hydration level, the DES–water mixture is best described as an aqueous solution of DES components.
The liquid structure of the archetypal Deep Eutectic Solvent (DES) reline, a 1 : 2 molar mixture of choline chloride and urea, has been determined at 303 K. This is the first reported liquid-phase neutron diffraction experiment on a cholinium DES. H/D isotopic substitution is used to obtain differential neutron scattering cross sections, and an Empirical Potential Structure Refinement (EPSR) model is fitted to the experimental data. Radial distribution functions (RDFs) derived from EPSR reveal the presence of the anticipated hydrogen bonding network within the liquid, with significant ordering interactions not only between urea and chloride, but between all DES components. Spatial density functions (SDFs) are used to map the 3D structure of the solvent. Interestingly, choline is found to contribute strongly to this bonding network via the hydroxyl group, giving rise to a radially layered structure with ordering between all species. The void size distribution function calculated for reline suggests that the holes present within DESs are far smaller than previously suggested by hole theory. These observations have important implications in the future development of these ‘designer solvents’.
Improvements in the efficiency of combustion within a vehicle can lead to reductions in the emission of harmful pollutants and increased fuel efficiency. Gas sensors have a role to play in this process, since they can provide real time feedback to vehicular fuel and emissions management systems as well as reducing the discrepancy between emissions observed in factory tests and ‘real world’ scenarios. In this review we survey the current state-of-the-art in using porous materials for sensing the gases relevant to automotive emissions. Two broad classes of porous material – zeolites and metal–organic frameworks (MOFs) – are introduced, and their potential for gas sensing is discussed. The adsorptive, spectroscopic and electronic techniques for sensing gases using porous materials are summarised. Examples of the use of zeolites and MOFs in the sensing of water vapour, oxygen, NOx, carbon monoxide and carbon dioxide, hydrocarbons and volatile organic compounds, ammonia, hydrogen sulfide, sulfur dioxide and hydrogen are then detailed. Both types of porous material (zeolites and MOFs) reveal great promise for the fabrication of sensors for exhaust gases and vapours due to high selectivity and sensitivity. The size and shape selectivity of the zeolite and MOF materials are controlled by variation of pore dimensions, chemical composition (hydrophilicity/hydrophobicity), crystal size and orientation, thus enabling detection and differentiation between different gases and vapours.
In the past few years there has been a growth in the use of nanoparticles for stabilizing lipid membranes that contain embedded proteins. These bionanoparticles provide a solution to the challenging problem of membrane protein isolation by maintaining a lipid bilayer essential to protein integrity and activity. We have previously described the use of an amphipathic polymer (poly(styrene-co-maleic acid), SMA) to produce discoidal nanoparticles with a lipid bilayer core containing the embedded protein. However the structure of the nanoparticle itself has not yet been determined. This leaves a major gap in understanding how the SMA stabilizes the encapsulated bilayer and how the bilayer relates physically and structurally to an unencapsulated lipid bilayer. In this paper we address this issue by describing the structure of the SMA lipid particle (SMALP) using data from small angle neutron scattering (SANS), electron microscopy (EM), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), differential scanning calorimetry (DSC) and nuclear magnetic resonance spectroscopy (NMR). We show that the particle is disc shaped containing a polymer “bracelet” encircling the lipid bilayer. The structure and orientation of the individual components within the bilayer and polymer are determined showing that styrene moieties within SMA intercalate between the lipid acyl chains. The dimensions of the encapsulated bilayer are also determined and match those measured for a natural membrane. Taken together, the description of the structure of the SMALP forms the foundation for future development and applications of SMALPs in membrane protein production and analysis.
The functionalised metal–organic framework MIL-101(Cr)-NH2, containing 2-aminobenzene-1,4-dicarboxylate as the linker, has been synthesised. A new tandem post-synthetic modification strategy involving diazotisation as the first step has been developed and used to introduce halo- and azo dye-functional groups into the pores.
1 August 2018 in Current Opinion in Green and Sustainable Chemistry