Rolfe G. Petschek

The effect of different analyte diffusion/adsorption protocols was studied which is often overlooked in surface-enhanced Raman scattering (SERS) technique. Three protocols: highly concentrated dilution (HCD) protocol, half–half dilution (HHD) protocol and layered adsorption (LA) protocol were studied and the SERS substrates were monolayer films of 80 nm Ag nanoparticles (NPs) which were modified by polyvinylpyrrolidone. The diffusion/adsorption mechanisms were modelled using the diffusion equation and the electromagnetic field distribution of two adjacent Ag NPs was simulated by the finite-different time-domain method. All experimental data and theoretical analysis suggest that different diffusion/adsorption behaviour of analytes will cause different SERS signal enhancements. HHD protocol could produce the most uniform and reproducible samples, and the corresponding signal intensity of the analyte is the strongest. This study will help to understand and promote the use of SERS technique in quantitative analysis.

A novel structure was observed below the smectic-A–smectic-C phase transition in a very thin open cell having an air interface above and enforced planar anchoring at the substrate below. The structure appears as periodic dark and light streaks running perpendicular to the oily streaks, which are present in the smectic-A phase [D. Coursault et al., Soft Matter, 2016, 12, 678]. These new streaks, which we call “soapy streaks”, form by extending from one oily streak to the next in discrete steps, eliminating optical evidence at visible wavelengths of the oily streaks. At lower temperatures the streaks can undulate and exhibit a sawtooth-like structure; such a structure is chiral in two dimensions. A possible scenario for the origin of these streaks is presented.

Ferrofluids are familiar as colloidal suspensions of ferromagnetic nanoparticles in aqueous or organic solvents. The dispersed particles are randomly oriented but their moments become aligned if a magnetic field is applied, producing a variety of exotic and useful magnetomechanical effects. A longstanding interest and challenge has been to make such suspensions macroscopically ferromagnetic, that is having uniform magnetic alignment in the absence of a field. Here we report a fluid suspension of magnetic nanoplates that spontaneously aligns into an equilibrium nematic liquid crystal phase that is also macroscopically ferromagnetic. Its zero-field magnetization produces distinctive magnetic self-interaction effects, including liquid crystal textures of fluid block domains arranged in closed flux loops, and makes this phase highly sensitive, with it dramatically changing shape even in the Earth’s magnetic field.

Chiral periodic mesoporous organosilica (PMO) materials have been shown to deracemise a configurationally achiral, but conformationally racemic liquid crystal in which the PMO is embedded. In particular, application of an electric field E in the liquid crystal’s smectic-A phase results in a rotation of the liquid-crystal director by an angle proportional to E, which is detected optically – this is the so-called ‘electroclinic’ effect. Here we present results from electroclinic measurements as a function of frequency and temperature, which allow us to distinguish the component of optical signal that arises from liquid-crystal chirality induced within the PMO’s chiral pores from that induced just outside the silica colloids. Our central result is that the overwhelming source of our electrooptic signal emanates from outside the PMO, and that the contribution from the liquid crystal embedded in the chiral pores is much smaller and below the noise level. GRAPHICAL ABSTRACT

A polyimide substrate was scribed using the stylus of an atomic force microscope, then covered with a nematic liquid crystal. The fiber from a near field scanning optical microscope was immersed into the liquid crystal and rastered approximately 80 nm above the surface, thereby obviating smearing effects that occur in thicker samples. By appropriate averaging of multiple data sets, a histogram of the “frozen-in” director deviation Δφ from the average easy axis was obtained, having a full-width-half-maximum of ∼0.02 rad. Additionally, the spatial autocorrelation function of Δφ was extracted, where the primary correlation length was found to be comparable to, but larger than, the liquid crystal's extrapolation length. A secondary characteristic length scale of a few μm was observed, and is thought to be an artifact due to material ejection during the scribing process. Our results demonstrate the utility of nanoscale imaging of the interface behavior inside the liquid crystal.

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A macroscopic helical twist is imposed on an achiral nematic liquid crystal by controlling the azimuthal alignment directions at the two substrates. On application of an electric field the director rotates in the substrate plane. This electroclinic effect, which requires the presence of chirality, is strongest at the two substrates and increases with increasing imposed twist distortion. We present a simple model involving a trade-off among bulk elastic energy, surface anchoring energy, and deracemization entropy that suggests the large equilibrium director rotation induces a deracemization of chiral conformations in the molecules—effectively “top-down” chiral induction—quantitatively consistent with experiment.