John Harden

Nature-inspired light-harvesting liquid crystalline porphyrins for organic photovoltaics

A new class of nanoscale light‐harvesting discotic liquid crystalline porphyrins, with the same basic structure of the best photoreceptor in nature (chlorophyll), was synthesized. These materials can be exceptionally aligned into a highly ordered architecture in which the columns formed by intermolecular π–π stacking are spontaneously perpendicular to the substrate. The homeotropic alignment, well confirmed by synchrotron X‐ray diffraction, could not only provide the most efficient pathway for hole conduction along the columnar axis crossing the device thickness, but also offer the largest area to the incident light for optimized light harvesting. Their preliminary photocurrent generation and photovoltaic performances were also demonstrated. The results provide new and efficient pathways to the development of organic photovoltaics by using homeotropically aligned liquid crystal thin films.

Piezoelectricity of phospholipids: a possible mechanism for mechanoreception and magnetoreception in biology

We show that phospholipids, which are the main constituents of cell membranes, are piezoelectric. This was done by periodically shearing and compressing films of hydrated l‐α‐phosphatidylcholine, inducing a tilt of the molecules with respect to the bilayer’s normal, which produced an electric current perpendicular to the tilt plane, corresponding to a polarisation of about 300 nC cm−2 at 5° of tilt. We also measured electric currents induced by an alternating magnetic field of less than 100 G in hydrated phospholipids doped with 0.5 wt% of ferrofluid of magnetite (Fe3O4) nanoparticles. A discussion of possible implications of these effects on biophysical processes is also provided.

Bent-Core Liquid Crystal Elastomers

Liquid crystal (LC) elastomers with bent-core side-groups incorporate the properties of bent-core liquid crystals in a flexible and self-supporting polymer network. Bent-core liquid crystal elastomers (BCEs) with uniform alignment were prepared by attaching a reactive bent-core LC to poly(hydrogenmethylsiloxane) and crosslinking with a divinyl crosslinker. Phase behavior studies indicate a nematic phase over a wide temperature range that approaches room temperature, and thermoelastic measurements show that these BCEs can reversibly change their length by more than a factor of two upon heating and cooling. Small-angle X-ray scattering studies reveal multiple, broad low-angle peaks consistent with short-range smectic C order of the bent-core side groups. A comparison of these patterns with predictions of a Landau model for short-range smectic C order shows that the length scale for smectic ordering in BCEs is similar to that seen in pure bent-core LCs. The combination of rubber elasticity and smectic ordering of the bent-core side groups suggests that BCEs may be promising materials for sensing, actuating, and other advanced applications.

Direct piezoelectric responses of soft composite fiber mats

Recently soft fiber mats electrospun from solutions of Barium Titanate (BT) ferroelectric ceramics particles and polylactic acid (PLA) were found to have large (d33 ∼ 1 nm/V) converse piezoelectric signals offering a myriad of applications ranging from active implants to smart textiles. Here, we report direct piezoelectric measurements (electric signals due to mechanical stress) of the BT/PLA composite fiber mats at several BT concentrations. A homemade testing apparatus provided AC stresses in the 50 Hz-1.5 kHz-frequency range. The piezoelectric constant d33 ∼ 0.5 nC/N and the compression modulus Y ∼ 104–105 Pa found are in agreement with the prior converse piezoelectric and compressibility measurements. Importantly, the direct piezoelectric signal is large enough to power a small LCD by simple finger tapping of a 0.15 mm thick 2-cm2 area mat. We propose using these mats in active Braille cells and in liquid crystal writing tablets.

Piezoelectric fiber mats containing polar rod-shaped pigment particles

We demonstrate converse piezoelectric behavior of electrospun polylactic acid (PLA) fiber mats containing anisometric pigment nanoparticles (Novoperm Carmine HF3C). The effective piezoelectric constant of the fiber mats was estimated to be 2 nm V−1. These findings suggest polarity of the pigment particles obtained by a milling process. Transient electric current measurements were conducted to test the residual polarization of the particles. Piezoelectric fiber mats may be utilized to make colorful electro-active fiber mats and wearable smart clothing.

Extraordinary properties of nematic phases of bent-core liquid crystals

We briefly review systematic and comprehensive studies on several chlorine-substituted bent-core liquid crystal materials in their nematic phases. The results, in comparison to rod-shaped molecules, are both extraordinary and technologically significant. Specifically: a) Electrohydrodynamic instabilities provide unique patterns including well defined, periodic stripes and optically isotropic structures. b) Rheological measurements using different probe techniques (dynamic light scattering, pulsed magnetic field, electrorotation) reveal that the ratio of the flow and rotational viscosities are over two orders of magnitudes larger in bentcore than in calamitic materials which proves that the molecule shape and not its size is responsible for this behaviour. c) Giant flexoelectric response, as measured by dynamic light scattering and by directly probing the induced current when the material is subject to oscillatory bend deformation, turns out to be more than three orders of magnitude larger than in calamitics and 50 times larger than molecular shape considerations alone would predict. The magnitude of this effect renders these materials as promising candidates for efficient conversion between mechanical and electrical energy. d) The converse of this effect when the bent-core material sandwiched between plastic substrates 4 times thicker than the liquid crystal material provided displacements in the range of 100nm that is sensitive to the polarity of the applied field thus suggesting applications as beam steering and precision motion controls.