Proton conductivity in ampullae of Lorenzini jelly.

In 1678, Stefano Lorenzini first described a network of organs of unknown function in the torpedo ray-the ampullae of Lorenzini (AoL). An individual ampulla consists of a pore on the skin that is open to the environment, a canal containing a jelly and leading to an alveolus with a series of electrosensing cells. The role of the AoL remained a mystery for almost 300 years until research demonstrated that skates, sharks, and rays detect very weak electric fields produced by a potential prey. The AoL jelly likely contributes to this electrosensing function, yet the exact details of this contribution remain unclear. We measure the proton conductivity of the AoL jelly extracted from skates and sharks. The room-temperature proton conductivity of the AoL jelly is very high at 2 ± 1 mS/cm. This conductivity is only 40-fold lower than the current state-of-the-art proton-conducting polymer Nafion, and it is the highest reported for a biological material so far. We suggest that keratan sulfate, identified previously in the AoL jelly and confirmed here, may contribute to the high proton conductivity of the AoL jelly with its sulfate groups-acid groups and proton donors. We hope that the observed high proton conductivity of the AoL jelly may contribute to future studies of the AoL function.

A Palladium-Binding Deltarhodopsin for Light-Activated Conversion of Protonic to Electronic Currents.

Fusion of a palladium-binding peptide to an archaeal rhodopsin promotes intimate integration of the lipid-embedded membrane protein with a palladium hydride protonic contact. Devices fabricated with the palladium-binding deltarhodopsin enable light-activated conversion of protonic currents to electronic currents with on/off responses complete in seconds and a nearly tenfold increase in electrical signal relative to those made with the wild-type protein.

Proton mediated control of biochemical reactions with bioelectronic pH modulation.

In Nature, protons (H(+)) can mediate metabolic process through enzymatic reactions. Examples include glucose oxidation with glucose dehydrogenase to regulate blood glucose level, alcohol dissolution into carboxylic acid through alcohol dehydrogenase, and voltage-regulated H(+) channels activating bioluminescence in firefly and jellyfish. Artificial devices that control H(+) currents and H(+) concentration (pH) are able to actively influence biochemical processes. Here, we demonstrate a biotransducer that monitors and actively regulates pH-responsive enzymatic reactions by monitoring and controlling the flow of H(+) between PdHx contacts and solution. The present transducer records bistable pH modulation from an "enzymatic flip-flop" circuit that comprises glucose dehydrogenase and alcohol dehydrogenase. The transducer also controls bioluminescence from firefly luciferase by affecting solution pH.

Two-terminal protonic devices with synaptic-like short-term depression and device memory.

Two-terminal protonic devices with PdHx proton conducting contacts and a Nafion channel achieve 25 ms spiking, short term depression, and low-energy memory switching.

A cryogenic scattering-type scanning near-field optical microscope.

Scattering-type scanning near-field optical microscopy (s-SNOM) provides few nanometer optical spatial resolution and is compatible with nearly any form of linear and nonlinear optical spectroscopy. We have developed a versatile s-SNOM instrument operating under cryogenic and variable temperature (∼20-500 K) and compatible with high magnetic fields (up to 7 T). The instrument features independent tip and sample scanning and free-space light delivery with an integrated off-axis parabolic mirror for tip-illumination and signal collection with a numerical aperture of N.A. = 0.45. The optics operate from the UV to THz range allowing for continuous wave, broadband, and ultrafast s-SNOM spectroscopy, including different variants of tip-enhanced spectroscopy. We discuss the instrument design, implementation, and demonstrate its performance with mid-infrared Drude response s-SNOM probing of the domain formation associated with the metal-insulator transitions of VO2 (TMIT ≃ 340 K) and V2O3 (TMIT ≃ 150 K). This instrument enables the study of mesoscopic order and domains of competing quantum phases in correlated electron materials over a wide range of controlled electric and magnetic fields, strain, current, and temperature.

Infrared near-field spectroscopy of trace explosives using an external cavity quantum cascade laser.

Utilizing a broadly-tunable external cavity quantum cascade laser for scattering-type scanning near-field optical microscopy (s-SNOM), we measure infrared spectra of particles of explosives by probing characteristic nitro-group resonances in the 7.1-7.9 µm wavelength range. Measurements are presented with spectral resolution of 0.25 cm(-1), spatial resolution of 25 nm, sensitivity better than 100 attomoles, and at a rapid acquisition time of 90 s per spectrum. We demonstrate high reproducibility of the acquired s-SNOM spectra with very high signal-to-noise ratios and relative noise of <0.02 in self-homodyne detection.