Enhanced Chiral Sensing at the Few-Molecule Level Using Negative Index Metamaterial Plasmonic Nanocuvettes.

Chirality is a fundamental property of biological molecules and some pharmaceutical molecules. Chiral molecules have a pair of chiral isomers (enantiomers) with opposite handedness. Although both enantiomers of the same molecule have identical chemical and physical properties, one enantiomer may be toxic to living organisms while the other one is harmless. The detection of these enantiomers is done using their small differential absorption between right and left circularly polarized light, known as circular dichroism (CD). Considering the macroscopic size of these molecules, combined with their small differential absorption, the obtained CD signal is very small, imposing a severe limitation on the minimal concentration that can be detected. Chiral plasmonic and metamaterial structures have been used to enhance the sensitivity of CD measurements by orders of magnitude through chiral density hot spots (super chiral fields). However, the large background signal due to these structures' intrinsic chirality limits the effectiveness of these methods. Contrary to absorption-based chiral sensing measurements (CD), fluorescence detection circular dichroism (FDCD) sensing can greatly improve chiral measurement sensitivity, down to the ultimate limit of a few and even a single chiral molecule. Like differential absorption, differential fluorescence also produces a weak signal at the few-chiral-molecule limit. However, here we demonstrate a negative-index metamaterial (NIM) cavity that acts as a "plasmonic nanocuvette" with globally enhanced volume super chiral fields. Moreover, the achiral structure of the plasmonic nanocuvette allows for completely background-free chiral sensing. We show that with NIM-cavity-enhanced FDCD, we can detect as low as a few tens of chiral molecules, well within the zeptomole range.

Tunable Plasmonic Nanohole Arrays Actuated by a Thermoresponsive Hydrogel Cushion.

New plasmonic structure with actively tunable optical characteristics based on thermoresponsive hydrogel is reported. It consists of a thin, template-stripped Au film with arrays of nanoholes that is tethered to a transparent support by a cross-linked poly(N-isopropylacrylamide) (pNIPAAm)-based polymer network. Upon a contact of the porous Au surface with an aqueous environment, a rapid flow of water through the pores enables swelling and collapsing of the underlying pNIPAAm network. The swelling and collapsing could be triggered by small temperature changes around the lower critical solution temperature (LCST) of the hydrogel. The process is reversible, and it is associated with strong refractive index changes of Δn ∼ 0.1, which characteristically alters the spectrum of surface plasmon modes supported by the porous Au film. This approach can offer new attractive means for optical biosensors with flow-through architecture and actively tunable plasmonic transmission optical filters.

Reversibly tunable plasmonic bandgap by responsive hydrogel grating.

Reversible actuating of surface plasmon propagation by responsive hydrogel grating is reported. Thermo-responsive poly(N-isopropylacrylamide)-based (pNIPAAm) hydrogel nanostructure was designed and tethered to a gold surface in order to switch on and off Bragg scattering of surface plasmons which is associated with an occurrence of a bandgap in their dispersion relation. pNIPAAm-based grating with a period around 280 nm was prepared by using photo-crosslinkable terpolymer and laser interference lithography and it was brought in contact with water. The temperature induced swelling and collapse of pNIPAAm hydrogel grating strongly modulates its refractive index (Δn~0.1) which leads to the reversible opening and closing of a plasmonic bandgap. The experiments demonstrate partial opening of a bandgap with the width of 12 nm at wavelength around 800 nm where SPR exhibited the spectral width of about 75 nm.

Cerebral venous sinus thrombosis with autoimmune thyroiditis.

Cerebral Venous Thrombosis (CVT) is a multifactorial condition which is described as idiopathic in 12.5% of patients. Hyperthyroidism has been associated with CVT in many case reports, and increased levels of factor VIII and von Willebrand factor (vWF) have been proposed as the possible link in this association, but only few rare case reports have described an association of hypothyroidism with CVT. We report here a case of autoimmune thyroiditis presenting with CVT.