Chirality-induced avalanche magnetization of magnetite by an RNA precursor.

Homochirality is a hallmark of life on Earth. To achieve and maintain homochirality within a prebiotic network, the presence of an environmental factor acting as a chiral agent and providing a persistent chiral bias to prebiotic chemistry is highly advantageous. Magnetized surfaces are prebiotically plausible chiral agents due to the chiral-induced spin selectivity (CISS) effect, and they were utilized to attain homochiral ribose-aminooxazoline (RAO), an RNA precursor. However, natural magnetic minerals are typically weakly magnetized, necessitating mechanisms to enhance their magnetization for their use as effective chiral agents. Here, we report the magnetization of magnetic surfaces by crystallizing enantiopure RAO, whereby chiral molecules induce a uniform surface magnetization due to the CISS effect, which spreads across the magnetic surface akin to an avalanche. Chirality-induced avalanche magnetization enables a feedback between chiral molecules and magnetic surfaces, which can amplify a weak magnetization and allow for highly efficient spin-selective processes on magnetic minerals.

Does Coherence Affect the Multielectron Oxygen Reduction Reaction?

The oxygen reduction reaction (ORR) is the key for oxygen-based respiration and the operation of fuel cells. It involves the transmission of two pairs of electrons. We probed what type of interaction between the electrons is required to enable their efficient transfer into the oxygen. We show experimentally that the transfer of the electrons is controlled by the "hidden property" and present a theoretical model suggesting that it is related to coherent phase relations between the two electrons. Using spin polarization electrochemical measurements, with electrodes coated with different thicknesses of chiral coating, we confirm the special relation between the electrons. This relation is destroyed by multiple scattering events that result in the formation of hydrogen peroxide, which indicates a reduction in the ORR efficiency. Another indication for the possible role of coherence is the fluctuations in the reaction efficiency as a function of thickness of the chiral coated electrode.

Easily processable spin filters: exploring the chiral induced spin selectivity of bowl-shaped chiral subphthalocyanines.

High spin polarization (SP) in studies of chiral induced spin selectivity (CISS) is only observed when chiral molecules are properly organized. This is generally achieved by using anchoring groups or complex supramolecular polymers. A new class of spin filters based on bowl-shaped aromatics is reported, which form high-quality thin-films by simply spin-coating and displaying high spin filtering properties. In particular, we fabricate devices containing enantiopure tribromo-subphthalocyanines (SubPcs), and measure the CISS effect by means of magnetic conductive probe atomic force microscopy (mc-AFM). Circular dichroism and AFM experiments reveal that the resulting thin-film presents a well-ordered chiral structure. Remarkably, the resulting devices show SPs as high as ca. 50%, which are comparable to those obtained by using the current complex methodologies. These results boost the potential of bowl-shaped aromatics as easily processable spin filters, opening new frontiers toward realistic and efficient spintronic devices based on the CISS effect.

Optical Activity and Spin Polarization: The Surface Effect.

Chirality ('handedness') is a property that underlies a broad variety of phenomena in nature. Chiral molecules appear in two forms, and each is a mirror image of the other, the two enantiomers. The chirality of molecules is associated with their optical activity, and circular dichroism is commonly applied to identify the handedness of chiral molecules. Recently, the chiral induced spin selectivity (CISS) effect was established, according to which transfer of electrons within chiral molecules depends on the electron's spin. Which spin is preferred depends on the handedness of the chiral molecule and the direction of motion of the electron. Several experiments in the past indicated that there may be a relation between the optical activity of the molecules and their spin selectivity. Here, we show that for a molecule containing several stereogenic axes, when adsorbed on a metal substrate, the peaks in the CD spectra have the same signs for the two enantiomers. This is not the case when the molecules are adsorbed on a nonmetallic substrate or dissolved in solution. Quantum chemical simulations are able to explain the change in the CD spectra upon adsorption of the molecules on conductive and nonconductive surfaces. Surprisingly, the CISS properties are similar for the two enantiomers when adsorbed on the metal substrate, while when the molecules are adsorbed on nonmetallic surface, the preferred spin depends on the molecule handedness. This correlation between the optical activity and the CISS effect indicates that the CISS effect relates to the global polarizability of the molecule.

Spin-induced asymmetry reaction-The formation of asymmetric carbon by electropolymerization.

We describe the spin polarization-induced chirogenic electropolymerization of achiral 2-vinylpyridine, which forms a layer of enantioenhanced isotactic polymer on the electrode. The product formed is enantioenriched in asymmetric carbon polymer. To confirm the chirality of the polymer film formed on the electrode, we also measured its electron spin polarization properties as a function of its thickness. Two methods were used: First, spin polarization was measured by applying magnetic contact atomic force microscopy, and second, magnetoresistance was assessed in a sandwich-like four-point contact structure. We observed high spin-selective electron transmission, even for a layer thickness of 120 nm. A correlation exists between the change in the circular dichroism signal and the change in the spin polarization, as a function of thickness. The spin-filtering efficiency increases with temperature.

Functionalization of amorphous SiO2 and 6H-SiC(0001) surfaces with benzo[ghi]perylene-1,2-dicarboxylic anhydride via an APTES linker.

The successful covalent functionalization of quartz and n-type 6H-SiC with organosilanes and benzo[ghi]perylene-1,2-dicarboxylic dye is demonstrated. In particular, wet-chemically processed self-assembled layers of aminopropyltriethoxysilane (APTES) and benzo[ghi]perylene-1,2-dicarboxylic anhydride are investigated. The structural and chemical properties of these layers are studied by contact angle measurements, attenuated total reflection infrared (ATR-IR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). The optical properties are measured by confocal microscopy. The wetting angles observed for the organic layers are α = 68° for the APTES-functionalized surface, while angles of α = 85° and 78° are determined for dye-functionalized quartz and 6H-SiC surfaces, respectively. However, not all amino groups of the APTES-functionalized surfaces react to bind dye molecules. Further dye functionalization is not uniform throughout the surface, showing different island sizes of the dye and including different chemical environments. The quartz surface exhibits a higher packing density of dyes than the 6H-SiC surface. The fluorescence lifetimes of the surface-attached dye show double exponential decays of about 1.4 and 4.2 ns, largely independent of the substrates.