Design of optoelectrodes for the remote imaging of cells and in situ electrochemical detection of neurosecretory events.

Optical fibers have opened avenues for remote imaging, bioanalyses and recently optogenetics. Besides, miniaturized electrochemical sensors have offered new opportunities in sensing directly redox neurotransmitters. The combination of both optical and electrochemical approaches was usually performed on the platform of microscopes or within microsystems. In this work, we developed optoelectrodes which features merge the advantages of both optical fibers and microelectrodes. Optical fiber bundles were modified at one of their extremity by a transparent ITO deposit. The electrochemical responses of these ITO-modified bundles were characterized for the detection of dopamine, epinephrine and norepinephrine. The analytical performances of the optoelectrodes were equivalent to the ones reported for carbon microelectrodes. The remote imaging of model neurosecretory PC12 cells by optoelectrodes was performed upon cell-staining with common fluorescent dyes: acridine orange and calcein-AM. An optoelectrode placed by micromanipulation at a few micrometers-distance from the cells offered remote images with single cell resolution. Finally, in situ electrochemical sensing was demonstrated by additions of K+-secretagogue solutions near PC12 cells under observation, leading to exocytotic events detected as amperometric spikes at the ITO surface. Such dual sensors should pave the way for in vivo remote imaging, optogenetic stimulation, and simultaneous detection of neurosecretory activities.

Superconducting Scanning Tunneling Microscope Tip to Reveal Sub-millielectronvolt Magnetic Energy Variations on Surfaces.

Combining the complex ordering ability of molecules with their local magnetic properties is a little-explored technique to tailor spin structures on surfaces. However, revealing the molecular geometry can be demanding. Nickelocene (Nc) molecules present a large spin-flip excitation leading to clear changes of conductance at the excitation-threshold bias. Using a superconducting tip, we have the energy resolution to detect small shifts of the Nc spin-flip excitation thresholds, permitting us to reveal the different individual environments of Nc molecules in an ordered layer. This knowledge allows us to reveal the adsorption configuration of a complex molecular structure formed by Nc molecules in different orientations and positions. As a consequence, we infer that Nc layers present a strong noncollinear magnetic-moment arrangement.

The Kondo Effect of a Molecular Tip As a Magnetic Sensor.

A single molecule offers to tailor and control the probing capability of a scanning tunneling microscope when placed on the tip. With the help of first-principles calculations, we show that on-tip spin sensitivity is possible through the Kondo ground state of a spin S = 1/2 cobaltocene molecule. When attached to the tip apex, we observe a reproducible Kondo resonance, which splits apart upon tuning the exchange coupling of cobaltocene to an iron atom on the surface. The spin-split Kondo resonance provides quantitative information on the exchange field and on the spin polarization of the iron atom. We also demonstrate that molecular vibrations cause the emergence of Kondo side peaks, which, unlike the Kondo resonance, are sensitive to cobaltocene adsorption.