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.
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).spin | chirality | enantioselectivity | biorecognition | exchange interaction T he wealth of information on protein structure has led to a much better understanding of the relation between structure and function in biomolecular processes and biological machines (1); however, basic phenomena remain unexplained in terms of structure-function relationships. Biorecognition, which is based on noncovalent interactions between molecules, retains mysteries, and its calculation evades first principles theory (2, 3). This failure suggests that some essential features are not included in our current description of these interactions (4,5). In this study, we show that charge polarization, which occurs in any biorecognition event, is accompanied by spin polarization for chiral molecules, an effect that is missing in most treatments. The subsequent magnetic interaction energies are small and therefore, play no significant role in the interactions; however, the spin polarization constrains the symmetry of the wave function(s) involved with the intermolecular interaction, so that significant differences in energy emerge for interactions between molecules of the same chirality and those of opposite chirality. Thus, this phenomenon may impact quantitative modeling of biorecognition events and contribute to our understanding of enantiorecognition in nature (6).Nucleotides, amino acids, and sugars are chiral; namely, they do not possess mirror plane symmetry but have symmetry like a "hand" (cheir in Greek). Force field models for the interaction between biomolecules do not account for spin polarization or include terms with chiral symmetry. Noncovalent interactions between biomolecules are commonly described classically by way of force fields, which are constructed from their geometrie...
Ferromagnets are commonly magnetized by either external magnetic fields or spin polarized currents. The manipulation of magnetization by spin-current occurs through the spin-transfer-torque effect, which is applied, for example, in modern magnetoresistive random access memory. However, the current density required for the spin-transfer torque is of the order of 1 × 106 A·cm−2, or about 1 × 1025 electrons s−1 cm−2. This relatively high current density significantly affects the devices' structure and performance. Here we demonstrate magnetization switching of ferromagnetic thin layers that is induced solely by adsorption of chiral molecules. In this case, about 1013 electrons per cm2 are sufficient to induce magnetization reversal. The direction of the magnetization depends on the handedness of the adsorbed chiral molecules. Local magnetization switching is achieved by adsorbing a chiral self-assembled molecular monolayer on a gold-coated ferromagnetic layer with perpendicular magnetic anisotropy. These results present a simple low-power magnetization mechanism when operating at ambient conditions.
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.
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.
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