Shlomo Yitzchaik

Spine-shaped gold protrusions improve the adherence and electrical coupling of neurons with the surface of micro-electronic devices

Interfacing neurons with micro- and nano-electronic devices has been a subject of intense study over the last decade. One of the major problems in assembling efficient neuro-electronic hybrid systems is the weak electrical coupling between the components. This is mainly attributed to the fundamental property of living cells to form and maintain an extracellular cleft between the plasma membrane and any substrate to which they adhere. This cleft shunts the current generated by propagating action potentials and thus reduces the signal-to-noise ratio. Reducing the cleft thickness, and thereby increasing the seal resistance formed between the neurons and the sensing surface, is thus a challenge and could improve the electrical coupling coefficient. Using electron microscopic analysis and field potential recordings, we examined here the use of gold micro-structures that mimic dendritic spines in their shape and dimensions to improve the adhesion and electrical coupling between neurons and micro-electronic devices. We found that neurons cultured on a gold-spine matrix, functionalized by a cysteine-terminated peptide with a number of RGD repeats, readily engulf the spines, forming tight apposition. The recorded field potentials of cultured Aplysia neurons are significantly larger using gold-spine electrodes in comparison with flat electrodes.

Silicon/Molecule Interfacial Electronic Modifications

Electronic structures at the silicon/molecule interface were studied by X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, inverse photoemission spectroscopy, and Kelvin probe techniques. The heterojunctions were fabricated by direct covalent grafting of a series of molecules (-C6H4-X, with X = NMe2, NH2, NO2, and Mo6 oxide cluster) onto the surface of four types of silicon substrates (both n- and p-type with different dopant densities). The electronic structures at the interfaces were thus systematically tuned in accordance with the electron-donating ability, redox capability, and/or dipole moment of the grafted molecules. The work function of each grafted surface is determined by a combination of the surface band bending and electron affinity. The surface band bending is dependent on the charge transfer between the silicon substrate and the grafted molecules, whereas electron affinity is dependent on the dipole moment of the grafted molecules. The contribution of each to the work function can be separated by a combination of the aforementioned analytical techniques. In addition, because of the relatively low molecular coverage on the surface, the contribution from the unreacted H-terminated surface to the work function was considered. The charge-transfer barrier of silicon substrates attached to different molecules exhibits a trend analogous to surface band bending effects, whereas the surface potential step exhibits properties analogous to electron affinity effects. These results provide a foundation for the utilization of organic molecule surface grafting as a means to tune the electronic properties of semiconductors and, consequently, to achieve controllable modulation of electronic characteristics in small semiconductor devices at future technology nodes.

MOLECULAR ELECTRONIC TUNING OF SI SURFACES

Abstract Assembling quinolinium-based chromophores on silicon surfaces provides a new route to electronic control over such semiconducting surfaces. The two-step process by which the molecules are grafted on to the surface involves first coupling the organic functionality to silicon, followed by chromophore anchoring. These synthetic steps are monitored by XPS, UV-Vis and FTIR spectroscopies. Using contact potential difference measurements we found that the electron affinity of the modified silicon is a function of the molecules dipole moment. The same technique shows a pronounced effect of the sub-nanometer siloxane-based, coupling-agent, layer by itself on the band bending and band-bending modification as function of chromophore adsorption.

Acetylcholine Detection at Micromolar Concentrations with the Use of an Artificial Receptor-Based Fluorescence Switch

An inclusion complex between water-soluble p-sulfocalix[n]arene (Cn, n=4, 6, 8) and the chromophore trans-4-[4-(dimethylamino)styryl]-1-methylpyridinium-p-toluenesulfonate (D) formed the basis for a highly sensitive sensor for the selective detection of neurotransmitter acetylcholine (ACh). Formation of the [Cn.D] complex (Ka=approximately 10(5) M(-1)) was accompanied by a drastic increase (up to 20-60-fold) in the chromophore relative quantum yield and by a large hypsochromic shift of the emission band maximum. The observed optical effects are fully reversible: ACh displaces the chromophore molecules from the calixarene cavity as shown by the reappearance of the free chromophore emission band. Formation and dissociation of the complex were studied by fluorescence, 1H NMR, and UV-vis absorption spectroscopies. The [Cn.D] complex is capable of sensing ACh selectively in solution at sub-micromolar concentrations. Immobilization of monocarboxyl p-sulfocalix[4]arene (C4m) on an oxide-containing silicon surface is in keeping with its properties, such as chromophore binding and the ability of the immobilized inclusion complex to detect ACh. The unique [Cn.D] complex optical switching paves the way for application in ACh imaging and optoelectronic sensing.

Searching for photochromic liquid crystals Spironaphthoxazine substituted with a mesogenic group

Abstract A number of photochromic spiropyrans and spirooxazines containing mesogenic groups were synthesized. Only one of them, spiro-indoline-naphthoxazine with mesogenic substituent, 4-(4-heptylbenzoyloxy)benzoyloxy in 5-position, revealed mesomorphic properties. Its phase behaviour, photochromism and alignment in the electric field was investigated. A structure of the mesophase is discussed.

Neurons culturing and biophotonic sensing using porous silicon

We report on culturing of Aplysia neurons on porous silicon substrates. Good adhesion of the neurons to the porous silicon substrate and a formation of neuron-semiconductor contact have been accomplished. Cultured neurons survived for at least one week on porous silicon showing normal passive membrane properties and generation of action potentials. We have investigated the possibility of using the photoluminescence from porous silicon for transducing neuronal activity into photonic signals. We found that photoluminescence quenching occurs for cathodic current polarization using aqueous salt-based liquid solution contact. The quenching process is due to diffusion of electrons into the porous silicon, giving rise to Auger nonradiative recombination in the silicon nanocrystallites. The decay time of the photoluminescence was found to be relatively slow due to diffusive nature of the process.

1,4;5,8-naphthalene-tetracarboxylic diimide derivatives as model compounds for molecular layer epitaxy

The physical properties and finite size effects observed in 1,4;5,8-naphthalene-tetracarboxylicdiimide (NTCDI)-based organic multilayers assembled by molecular layer epitaxy (MLE) are investigated by structure–property studies of low molecular weight model compounds. These molecules, aliphatic N,N′-dihexyl-NTCDI (1), N,N′-dihexadecyl-NTCDI (2) and aromatic N,N′-diphenyl-NTCDI (3), mimic the elemental building blocks of the solid-state heterostructures, NTCDI-based organic superlattices. Thermal analysis combined with polarized optical microscopy reveals that both 1 and 2 have polymorphic phases at an elevated temperature range. All model compounds show new absorption (abs.) and photoluminescence (PL) bathochromically shifted bands in concentrated (mM) solutions, as is also seen in MLE-derived organic superlattices. The strong tendency to aggregate and the photophysical properties of the model compounds are correlated with the PL and electrical field dependent electroluminescence (EL). This clarifies the structure-tunable emission by virtue of in-plane excitons in solid-state MLE structures. Finally, X-ray diffraction of single crystals of 1 and 3 reveal similar packing motifs for the molecules and the resulting solid-state MLE heterostructures.

Charge injection asymmetry: A new route to strong optical nonlinearity in poled polymers

Amorphous polymer films containing hyperpolarizable dye molecules are poled by an electric field applied parallel to the plane of the thin film. The resultant second harmonic generation is much stronger than predicted by the standard model of dipolar interactions, and furthermore indicates asymmetry both parallel and perpendicular to the poling field. These results are attributed to a new, efficient mechanism for the production of optical nonlinearity in poled films in which asymmetric charge injection into the polymer and its trapping by dye species sets up a charge gradient perpendicular to the direction of the external poling field.

Improved Neuronal Adhesion to the Surface of Electronic Device by Engulfment of Protruding Micro-Nails Fabricated on the Chip Surface

One of the major problems in assembling efficient neuro-electronic hybrids systems is the low electrical coupling between the components. This is mainly due to the low resistance, extracellular cleft formed between the cells plasma membrane and the substrate to which it adhere. This cleft shunts the current generated by the neuron, or the device and thus reduces the signal to noise ratio. To increase the clefts electrical resistance we fabricated gold micronails that protrude from the transistor gate surface. The micronails were functionalized by phagocytosis facilitating peptides. Cultured neurons readily engulf the functionalized micronails forming tight physical contact between the cells and the surface of the device.

Direct Detection of Molecular Biorecognition by Dipole Sensing Mechanism

This work investigates the feasibility of transducing molecular-recognition events into a measurable potentiometric signal. It is shown for the first time that biorecognition of acetylcholine (ACh) can be translated to conformational changes in the enzyme, acetylcholine-esterase (AChE), which in turn induces a measurable change in surface potential. Our results show that a highly sensitive detector for ACh can be obtained by the dilute assembly of AChE on a floating gate derived field effect transistor (FG-FET). A wide concentration range response is observed for ACh (10(-2)-10(-9)M) and for the inhibitor carbamylcholine CCh (10(-6)-10(-11)M). These enhanced sensitivities are modeled theoretically and explained by the combined response of the device to local pH changes and molecular dipole variations due to the enzyme-substrate recognition event.