Development of a high-frequency dielectric spectrometer using a portable vector network analyzer.

A simple and novel setup for high-frequency dielectric spectroscopy of materials has been developed using a portable vector network analyzer. The measurement principle is based on radio frequency reflectometry, and both its capabilities and limitations are discussed. The results obtained on a typical liquid crystal prove that the device can provide reliable spectra between 107 and 109 Hz, thus extending the capabilities of conventional impedance analyzers.

Collective and non-collective molecular dynamics in a ferroelectric nematic liquid crystal studied by broadband dielectric spectroscopy.

A great deal of effort has been recently devoted to the study of dielectric relaxation processes in ferroelectric nematic liquid crystals, yet their interpretation remains unclear. In this work, we present the results of broadband dielectric spectroscopy experiments of a prototypical ferroelectric nematogen in the frequency range 10 Hz-110 MHz at different electrode separations and under the application of DC bias fields. The results evidence a complex behavior in all phases due to the magnitude of polar correlations in these systems. The observed modes have been assigned to different relaxation mechanisms based on existing theoretical frameworks.

On the molecular origins of the ferroelectric splay nematic phase.

Nematic liquid crystals have been known for more than a century, but it was not until the 60s-70s that, with the development of room temperature nematics, they became widely used in applications. Polar nematic phases have been long-time predicted, but have only been experimentally realized recently. Synthesis of materials with nematic polar ordering at room temperature is certainly challenging and requires a deep understanding of its formation mechanisms, presently lacking. Here, we compare two materials of similar chemical structure and demonstrate that just a subtle change in the molecular structure enables denser packing of the molecules when they exhibit polar order, which shows that reduction of excluded volume is in the origin of the polar nematic phase. Additionally, we propose that molecular dynamics simulations are potent tools for molecular design in order to predict, identify and design materials showing the polar nematic phase and its precursor nematic phases.

Surface plasmon resonance immunosensor for ErbB2 breast cancer biomarker determination in human serum and raw cancer cell lysates.

A highly sensitive surface plasmon resonance (SPR) immunosensor for the important ErbB2 breast cancer biomarker has been developed. Optimization of the assay has been carried out, including signal enhancement employing gold nanoparticles (GNPs). The effect of the signal amplification of the GNPs has been also studied. The assay has been tested with clinically relevant matrices. Results in 50% human serum yielded a LOD of 180 pg mL(-1) which is a concentration 83 times lower than the clinical cut-off. Raw lysates from model breast cancer cell lines (SK-BR-3, MCF-7 and MDA-MB-436) have been also assayed and higher quantities of the ErbB2 protein were clearly observed in the ErbB2 over-expressing case (SK-BR-3). The results confirmed that the simple and highly sensitive SPR immunosensor represents a feasible tool for ErbB2 detection.

Surface plasmon resonance immunoassay for the detection of the TNFα biomarker in human serum.

A simple method for the detection of TNF-alpha protein biomarker in human serum with great sensitivity has been developed using a surface plasmon resonance biosensor. Signal amplification based on a sandwich immunoassay including gold nanoparticles was used. Detection in serum proved to be challenging due to high undesirable non-specific binding to the sensor surface stemming from the matrix nature of the sample. After optimization of the assay parameters and, in the case of serum, of a sample dilution buffer to minimize the non-specific binding, very low limits of detection were achieved: 11.6 pg/mL (211 fM) and 54.4 pg/mL (989 fM) for spiked buffer and human serum respectively. The amplification steps with high affinity biotinylated antibodies and streptavidin-fuctionalized nanoparticles greatly enhanced the signal with the advantage of additional specificity. Due to its simplicity and sensitivity, the immunoassay has proved feasible to be used for detection of low concentration biomarkers in real samples.

Real-time label-free surface plasmon resonance biosensing with gold nanohole arrays fabricated by nanoimprint lithography.

In this work we present a surface plasmon resonance sensor based on enhanced optical transmission through sub-wavelength nanohole arrays. This technique is extremely sensitive to changes in the refractive index of the surrounding medium which result in a modulation of the transmitted light. The periodic gold nanohole array sensors were fabricated by high-throughput thermal nanoimprint lithography. Square periodic arrays with sub-wavelength hole diameters were obtained and characterized. Using solutions with known refractive index, the array sensitivities were obtained. Finally, protein absorption was monitored in real-time demonstrating the label-free biosensing capabilities of the fabricated devices.

Laterally azo-bridged h-shaped ferroelectric dimesogens for second-order nonlinear optics: ferroelectricity and second harmonic generation.

Two classes of laterally azo-bridged H-shaped ferroelectric liquid crystals (FLCs), incorporating azobenzene and disperse red 1 (DR-1) chromophores along the FLC polar axes, were synthesized and characterized by polarized light microscopy, differential scanning calorimetry, 2D X-ray diffraction analysis, and electro-optical investigations. They represent the first H-shaped FLC materials exhibiting the ground-state, thermodynamically stable enantiotropic SmC* phase, i.e., ground-state ferroelectricity. Second harmonic generation measurements of one compound incorporating a DR-1 chromophore at the incident wavelength of 1064 nm give a nonlinear coefficient of d(22) = 17 pm/V, the largest nonlinear optics coefficient reported to date for calamitic FLCs. This value enables viable applications of FLCs in nonlinear optics.

Experimental test of curvature-driven dynamics in the phase ordering of a two dimensional liquid crystal.

We study electric field driven deracemization in an achiral liquid crystal through the formation and coarsening of chiral domains. It is proposed that deracemization in this system is a curvature-driven process. We test this prediction using the recently obtained exact result for the distribution of hull-enclosed areas in two-dimensional coarsening with nonconserved scalar order parameter dynamics [J. J. Arenzon et al., Phys. Rev. Lett. 98, 145701 (2007)]. The experimental data are in very good agreement with the theory. We thus demonstrate that deracemization in such bent-core liquid crystals belongs to the Allen-Cahn universality class, and that the exact formula, which gives us the statistics of domain sizes during coarsening, can also be used as a strict test for this dynamic universality class.

TTF-based bent-core liquid crystals.

The synthesis and characterization of bent-core liquid crystals which incorporate TTF groups is reported; different bent-core mesophases are induced depending on the molecular structure and properties derived from their compact packing have been studied.