Eyal Capua

Cold denaturation induces inversion of dipole and spin transfer in chiral peptide monolayers

Chirality-induced spin selectivity is a recently-discovered effect, which results in spin selectivity for electrons transmitted through chiral peptide monolayers. Here, we use this spin selectivity to probe the organization of self-assembled α-helix peptide monolayers and examine the relation between structural and spin transfer phenomena. We show that the α-helix structure of oligopeptides based on alanine and aminoisobutyric acid is transformed to a more linear one upon cooling. This process is similar to the known cold denaturation in peptides, but here the self-assembled monolayer plays the role of the solvent. The structural change results in a flip in the direction of the electrical dipole moment of the adsorbed molecules. The dipole flip is accompanied by a concomitant change in the spin that is preferred in electron transfer through the molecules, observed via a new solid-state hybrid organic–inorganic device that is based on the Hall effect, but operates with no external magnetic field or magnetic material.

The molecularly controlled semiconductor resistor: how does it work?

We examine the current response of molecularly controlled semiconductor devices to the presence of weakly interacting analytes. We evaluate the response of two types of devices, a silicon oxide coated silicon device and a GaAs/AlGaAs device, both coated with aliphatic chains and exposed to the same set of analytes. By comparing the device electrical response with contact potential difference and surface photovoltage measurements, we show that there are two mechanisms that may affect the underlying substrate, namely, formation of layers with a net dipolar moment and molecular interaction with surface states. We find that whereas the Si device response is mostly correlated to the analyte dipole, the GaAs device response is mostly correlated to interactions with surface states. Existence of a silicon oxide layer, whether native on the Si or deliberately grown on the GaAs, eliminates analyte interaction with the surface states.

Detection and quantification through a lipid membrane using the molecularly controlled semiconductor resistor.

The detection of covalent and noncovalent binding events between molecules and biomembranes is a fundamental goal of contemporary biochemistry and analytical chemistry. Currently, such studies are performed routinely using fluorescence methods, surface-plasmon resonance spectroscopy, and electrochemical methods. However, there is still a need for novel sensitive miniaturizable detection methods where the sample does not have to be transferred to the sensor, but the sensor can be brought into contact with the sample studied. We present a novel approach for detection and quantification of processes occurring on the surface of a lipid bilayer membrane, by monitoring the current change through the n-type GaAs-based molecularly controlled semiconductor resistor (MOCSER), on which the membrane is adsorbed. Since GaAs is susceptible to etching in an aqueous environment, a protective thin film of methoxysilane was deposited on the device. The system was found to be sensitive enough to allow monitoring changes in pH and in the concentration of amino acids in aqueous solution on top of the membrane. When biotinylated lipids were incorporated into the membrane, it was possible to monitor the binding of streptavidin or avidin. The device modified with biotin-streptavidin complex was capable of detecting the binding of streptavidin antibodies to immobilized streptavidin with high sensitivity and selectivity. The response depends on the charge on the analyte. These results open the way to facile electrical detection of protein-membrane interactions.

Chirality-induced spin polarization places symmetry constraints on biomolecular interactions.

Significance Chiral molecules are the building blocks of life. Although artificially, it is difficult to separate two different enantiomers of the same molecules; in nature, this process is efficient. This work proposes a mechanism for understanding this efficiency. In many bioprocesses, the interactions between molecules result from electron reorganization in the molecules, like that which occurs when an external electric field is applied. We show that the charge reorganization in chiral molecules is accompanied by a polarization of the spins associated with the displaced charge. The symmetry constraints imposed by the spin polarization may help account for the enantioselectivity. Calculations indicate that this contribution to the interaction energy for two molecules of the same handedness can be comparable with the available thermal energy. Noncovalent interactions between molecules are key for many biological processes. Necessarily, when molecules interact, the electronic charge in each of them is redistributed. Here, we show experimentally that, in chiral molecules, charge redistribution is accompanied by spin polarization. We describe how this spin polarization adds an enantioselective term to the forces, so that homochiral interaction energies differ from heterochiral ones. The spin polarization was measured by using a modified Hall effect device. An electric field that is applied along the molecules causes charge redistribution, and for chiral molecules, a Hall voltage is measured that indicates the spin polarization. Based on this observation, we conjecture that the spin polarization enforces symmetry constraints on the biorecognition process between two chiral molecules, and we describe how these constraints can lead to selectivity in the interaction between enantiomers based on their handedness. Model quantum chemistry calculations that rigorously enforce these constraints show that the interaction energy for methyl groups on homochiral molecules differs significantly from that found for heterochiral molecules at van der Waals contact and shorter (i.e., ∼0.5 kcal/mol at 0.26 nm).

Separation of enantiomers by their enantiospecific interaction with achiral magnetic substrates

Taking enantiomers for a spin There are two common ways to distinguish mirror-image molecules, or enantiomers. The first relies on their distinct interactions with circularly polarized light, the second on their interactions with a pure enantiomer of some other molecule. Now Banerjee-Ghosh et al. report a conceptually different approach to chiral resolution. Experiments showed that, depending on the direction of magnetization, chiral oligopeptides, oligonucleotides, and amino acids have enantiospecific differences in initial adsorption rates on ferromagnetic surfaces. This effect is attributed to enantiospecific induced spin polarization. Science, this issue p. 1331 Spin polarization of chiral molecules enhances the initial adsorption rate of one enantiomer onto a ferromagnetic substrate. It is commonly assumed that recognition and discrimination of chirality, both in nature and in artificial systems, depend solely on spatial effects. However, recent studies have suggested that charge redistribution in chiral molecules manifests an enantiospecific preference in electron spin orientation. We therefore reasoned that the induced spin polarization may affect enantiorecognition through exchange interactions. Here we show experimentally that the interaction of chiral molecules with a perpendicularly magnetized substrate is enantiospecific. Thus, one enantiomer adsorbs preferentially when the magnetic dipole is pointing up, whereas the other adsorbs faster for the opposite alignment of the magnetization. The interaction is not controlled by the magnetic field per se, but rather by the electron spin orientations, and opens prospects for a distinct approach to enantiomeric separations.

Injection of Spin-Polarized Electrons into a AlGaN/GaN Device from an Electrochemical Cell: Evidence for an Extremely Long Spin Lifetime

Spin-polarized electrons are injected from an electrochemical cell through a chiral self-assembled organic monolayer into a AlGaN/GaN device in which a shallow two-dimensional electron gas (2DEG) layer is formed. The injection is monitored by a microwave signal that indicates a coherent spin lifetime that exceeds 10 ms at room temperature. The signal was found to be magnetic field independent; however, it depends on the current of the injected electrons, on the length of the chiral molecules, and on the existence of 2DEG.

Application of a GaAs-Based Sensor for Detecting Hemoglobin in Gastrointestinal Environments

In clinical applications, inspection of the hemorrhagic spots in the gastrointestinal (GI) tract is a challenging task. The hybrid GaAs-based device, developed by us, has been successfully used for sensing hemoglobin (Hb) in biological solutions. In this paper, a new method and apparatus were applied for using the GaAs-based sensor to detect Hb in a mimicked gastrointestinal circumstance. A surface protection layer of polymerized thiolated silanes was deposited on the top of the device to obtain a chemical passivation coating against surface etching and to achieve bio-compatibility. A selective device functionalization was achieved by the subsequent adsorption of Hb antibodies on the top of the protection layer. An integrated sensor containing two different antibodies enabled examining its selectivity to purely Hb. In vitro testing of the sensor indicated that it is capable of discriminating fasted-state simulated intestinal fluids when the concentration of Hb was above

Single Nanoparticle Magnetic Spin Memristor

10~\mu \text{g}

Spin-Dependent Processes Measured without a Permanent Magnet

/mL. Moreover, the sensor was capable of detecting Hb in swine intestinal fluids with the same sensitivity. This paper verified the feasibility to apply the sensor in clinical use, by embedding it on different types of endoscopes, in order to localize GI bleeding with high precision and sensitivity.

Sensing Cellular Metabolic Activity via a Molecular-Controlled Semiconductor Resistor

There is an increasing demand for the development of a simple Si-based universal memory device at the nanoscale that operates at high frequencies. Spin-electronics (spintronics) can, in principle, increase the efficiency of devices and allow them to operate at high frequencies. A primary challenge for reducing the dimensions of spintronic devices is the requirement for high spin currents. To overcome this problem, a new approach is presented that uses helical chiral molecules exhibiting spin-selective electron transport, which is called the chiral-induced spin selectivity (CISS) effect. Using the CISS effect, the active memory device is miniaturized for the first time from the micrometer scale to 30 nm in size, and this device presents memristor-like nonlinear logic operation at low voltages under ambient conditions and room temperature. A single nanoparticle, along with Au contacts and chiral molecules, is sufficient to function as a memory device. A single ferromagnetic nanoplatelet is used as a fixed hard magnet combined with Au contacts in which the gold contacts act as soft magnets due to the adsorbed chiral molecules.