Acceleration of diffusion in ethylammonium nitrate ionic liquid confined between parallel glass plates

The bulk self diffusion of the ethylammonium cation and the nitrate anion can both be described by respective single diffusion coefficients. Diffusion of the anion is 1.7 times higher than that of the cation. This indicates no tight association of the ions in the ionic liquid. For the ethylammonium cation confined between glass plates the effective diffusion coefficient along, as well as normal to the confining glass plates is higher by a factor of 1.86 as compared to that in the bulk. The same time, NMR T2 relaxation of protons of NH3 group of the EA cation is faster by a factor of 22 than that in bulk. 2H NMR spectra of selectively labeled CH2 and CH3 groups of EA do not demonstrate any ordering of the EA between the glass plates. We suggested that these data favor a model where a bulk isotropic sponge like structure of EAN is saved in the confinement, but sizes of connecting channels increases. Those leads to faster translational diffusion and faster exchange processes of protons of NH3 group, in comparison with the bulk.Comment: 11 pages, 5 figures, 1 tabl

Feeling Small: Exploring the Tactile Perception Limits

The human finger is exquisitely sensitive in perceiving different materials, but the question remains as to what length scales are capable of being distinguished in active touch. We combine material science with psychophysics to manufacture and haptically explore a series of topographically patterned surfaces of controlled wavelength, but identical chemistry. Strain-induced surface wrinkling and subsequent templating produced 16 surfaces with wrinkle wavelengths ranging from 300 nm to 90 μm and amplitudes between 7 nm and 4.5 μm. Perceived similarities of these surfaces (and two blanks) were pairwise scaled by participants, and interdistances among all stimuli were determined by individual differences scaling (INDSCAL). The tactile space thus generated and its two perceptual dimensions were directly linked to surface physical properties – the finger friction coefficient and the wrinkle wavelength. Finally, the lowest amplitude of the wrinkles so distinguished was approximately 10 nm, demonstrating that human tactile discrimination extends to the nanoscale

Interfacial structuring of non-halogenated imidazolium ionic liquids at charged surfaces : effect of alkyl chain length

Control of the interfacial structures of ionic liquids (ILs) at charged interfaces is important to many of their applications, including in energy storage solutions, sensors and advanced lubrication technologies utilising electric fields. In the case of the latter, there is an increasing demand for the study of non-halogenated ILs, as many fluorinated anions have been found to produce corrosive and toxic halides under tribological conditions. Here, the interfacial structuring of a series of four imidazolium ILs ([C(n)C(1)Im]) of varying alkyl chain lengths (n = 5, 6, 7, 10), with a non-halogenated borate-based anion ([BOB]), have been studied at charged interfaces using sum frequency generation (SFG) spectroscopy and neutron reflectivity (NR). For all alkyl chain lengths, the SFG spectra show that the cation imidazolium ring responds to the surface charge by modifying its orientation with respect to the surface normal. In addition, the combination of SFG spectra with electrochemical NR measurements reveals that the longest alkyl chain length (n = 10) forms a bilayer structure at all charged interfaces, independent of the ring orientation. These results demonstrate the tunability of IL interfacial layers through the use of surface charge, as well as effect of the cation alkyl chain length, and provide valuable insight into the charge compensation mechanisms of ILs

A Motion Illusion Reveals Mechanisms of Perceptual Stabilization

Visual illusions are valuable tools for the scientific examination of the mechanisms underlying perception. In the peripheral drift illusion special drift patterns appear to move although they are static. During fixation small involuntary eye movements generate retinal image slips which need to be suppressed for stable perception. Here we show that the peripheral drift illusion reveals the mechanisms of perceptual stabilization associated with these micromovements. In a series of experiments we found that illusory motion was only observed in the peripheral visual field. The strength of illusory motion varied with the degree of micromovements. However, drift patterns presented in the central (but not the peripheral) visual field modulated the strength of illusory peripheral motion. Moreover, although central drift patterns were not perceived as moving, they elicited illusory motion of neutral peripheral patterns. Central drift patterns modulated illusory peripheral motion even when micromovements remained constant. Interestingly, perceptual stabilization was only affected by static drift patterns, but not by real motion signals. Our findings suggest that perceptual instabilities caused by fixational eye movements are corrected by a mechanism that relies on visual rather than extraretinal (proprioceptive or motor) signals, and that drift patterns systematically bias this compensatory mechanism. These mechanisms may be revealed by utilizing static visual patterns that give rise to the peripheral drift illusion, but remain undetected with other patterns. Accordingly, the peripheral drift illusion is of unique value for examining processes of perceptual stabilization

Disruption of Higher Order DNA Structures in Friedreich's Ataxia (GAA)n Repeats by PNA or LNA Targeting

Expansion of (GAA)n repeats in the first intron of the Frataxin gene is associated with reduced mRNA and protein levels and the development of Friedreich’s ataxia. (GAA)n expansions form non-canonical structures, including intramolecular triplex (H-DNA), and R-loops and are associated with epigenetic modifications. With the aim of interfering with higher order H-DNA (like) DNA structures within pathological (GAA)n expansions, we examined sequence-specific interaction of peptide nucleic acid (PNA) with (GAA)n repeats of different lengths (short: n=9, medium: n=75 or long: n=115) by chemical probing of triple helical and single stranded regions. We found that a triplex structure (H-DNA) forms at GAA repeats of different lengths; however, single stranded regions were not detected within the medium size pathological repeat, suggesting the presence of a more complex structure. Furthermore, (GAA)4-PNA binding of the repeat abolished all detectable triplex DNA structures, whereas (CTT)5-PNA did not. We present evidence that (GAA)4-PNA can invade the DNA at the repeat region by binding the DNA CTT strand, thereby preventing non-canonical-DNA formation, and that triplex invasion complexes by (CTT)5-PNA form at the GAA repeats. Locked nucleic acid (LNA) oligonucleotides also inhibited triplex formation at GAA repeat expansions, and atomic force microscopy analysis showed significant relaxation of plasmid morphology in the presence of GAA-LNA. Thus, by inhibiting disease related higher order DNA structures in the Frataxin gene, such PNA and LNA oligomers may have potential for discovery of drugs aiming at recovering Frataxin expression

Comparative review of human and canine osteosarcoma: morphology, epidemiology, prognosis, treatment and genetics

Osteosarcoma (OSA) is a rare cancer in people. However OSA incidence rates in dogs are 27 times higher than in people. Prognosis in both species is poor, with five year osteosarcoma survival rates in people not having improved in decades. For dogs, one year survival rates are only around ~45%. Improved and novel treatment regimens are urgently required to improve survival in both humans and dogs with OSA. Utilising information from genetic studies could assist in this in both species, with the higher incidence rates in dogs contributing to the dog population being a good model of human disease. This review compares the clinical characteristics, gross morphology and histopathology, aetiology, epidemiology, and genetics of canine and human osteosarcoma. Finally, the current position of canine osteosarcoma genetic research is discussed and areas for additional work within the canine population are identified

Ionic liquid lubrication : influence of ion structure, surface potential and sliding velocity

Colloid probe atomic force microscopy (AFM) has been employed to investigate the nanotribology of the ionic liquid (IL)–Au(111) interface. Data is presented for four ILs, 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([EMIM] FAP), 1-butyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([BMIM] FAP), 1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([HMIM] FAP) and 1-butyl-3-methylimidazolium iodide ([BMIM] I), at different Au(111) surface potentials. Lateral forces vary as a function of applied surface potential and ion structure because the composition of the confined ion layer changes from cation-enriched (at negative potentials) to mixed (at 0 V), and to anion-enriched (at positive potentials). ILs with FAP− anions all exhibit similar nanotribology: low friction at negative potentials and higher friction at positive potentials. [BMIM] I displays the opposite behaviour, as an I⁻ anion-enriched layer is more lubricating than either the [BMIM]⁺ or FAP^- layers. The effect of cation charged group (charge-delocalised versus charged-localised) was investigated by comparing [BMIM] FAP with 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate ([Py] FAP). [BMIM] FAP is less lubricating at negative potentials, but more lubricating at positive potentials. This indicated that even at positive potentials the cation concentration in the boundary layer is sufficiently high to influence lubricity. The influence of sliding velocity on lateral force was investigated for the [EMIM] FAP–Au(111) system. At neutral potentials the behaviour is consistent with a discontinuous sliding process. When a positive or negative potential bias is applied, this effect is less pronounced as the colloid probe slides along a better defined ion plane