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There is increasing interest in the study of chiral degrees of freedom occurring in matter and in electromagnetic fields. Opportunities in quantum sciences will likely exploit two main areas that are the focus of this Review: (1) recent observations of the chiral-induced spin selectivity (CISS) effect in chiral molecules and engineered nanomaterials and (2) rapidly evolving nanophotonic strategies designed to amplify chiral light-matter interactions. On the one hand, the CISS effect underpins the observation that charge transport through nanoscopic chiral structures favors a particular electronic spin orientation, resulting in large room-temperature spin polarizations. Observations of the CISS effect suggest opportunities for spin control and for the design and fabrication of room-temperature quantum devices from the bottom up, with atomic-scale precision and molecular modularity. On the other hand, chiral-optical effects that depend on both spin- and orbital-angular momentum of photons could offer key advantages in all-optical and quantum information technologies. In particular, amplification of these chiral light-matter interactions using rationally designed plasmonic and dielectric nanomaterials provide approaches to manipulate light intensity, polarization, and phase in confined nanoscale geometries. Any technology that relies on optimal charge transport, or optical control and readout, including quantum devices for logic, sensing, and storage, may benefit from chiral quantum properties. These properties can be theoretically and experimentally investigated from a quantum information perspective, which has not yet been fully developed. There are uncharted implications for the quantum sciences once chiral couplings can be engineered to control the storage, transduction, and manipulation of quantum information. This forward-looking Review provides a survey of the experimental and theoretical fundamentals of chiral-influenced quantum effects and presents a vision for their possible future roles in enabling room-temperature quantum technologies.

The combination of photonics and spintronics opens new ways to transfer and process information. It is shown here that in systems in which organic molecules and semiconductor nanoparticles are combined, matching these technologies results in interesting new phenomena. We report on light induced and spin-dependent charge transfer process through helical oligopeptide-CdSe nanoparticles' (NPs) architectures deposited on ferromagnetic substrates with small coercive force (∼100-200 Oe). The spin control is achieved by the application of the chirality-induced spin-dependent electron transfer effect and is probed by two different methods: spin-controlled electrochemichemistry and photoluminescence (PL) at room temperature. The injected spin could be controlled by excitation of the nanoparticles. By switching the direction of the magnetic field of the substrate, the PL intensity could be alternated.

Controlled reduction of oxygen is important for developing clean energy technologies, such as fuel cells, and is vital to the existence of aerobic organisms. The process starts with oxygen in a triplet ground state and ends with products that are all in singlet states. Hence, spin constraints in the oxygen reduction must be considered. Here, we show that the electron transfer efficiency from chiral electrodes to oxygen (oxygen reduction reaction) is enhanced over that from achiral electrodes. We demonstrate lower overpotentials and higher current densities for chiral catalysts versus achiral ones. This finding holds even for electrodes composed of heavy metals with large spin–orbit coupling. The effect results from the spin selectivity conferred on the electron current by the chiral assemblies, the chiral-induced spin selectivity effect. [ABSTRACT FROM AUTHOR]

The chiral-induced spin selectivity (CISS) effect entails spin-selective electron transmission through chiral molecules. In the present study, the spin filtering ability of chiral, helical oligopeptide monolayers of two different lengths is demonstrated using magnetic conductive probe atomic force microscopy. Spin-specific nanoscale electron transport studies elucidate that the spin polarization is higher for 14-mer oligopeptides than that of the 10-mer. We also show that the spin filtering ability can be tuned by changing the tip-loading force applied on the molecules. The spin selectivity decreases with increasing applied force, an effect attributed to the increased ratio of radius to pitch of the helix upon compression and increased tilt angles between the molecular axis and the surface normal. The method applied here provides new insights into the parameters controlling the CISS effect. [ABSTRACT FROM AUTHOR]

Chirality in life has been preserved throughout evolution. It has been assumed that the main function of chirality is its contribution to structural properties. In the past two decades, however, it has been established that chiral molecules possess unique electronic properties. Electrons that pass through chiral molecules, or even charge displacements within a chiral molecule, do so in a manner that depends on the electron's spin and the molecule's enantiomeric form. This effect, referred to as chiral induced spin selectivity (CISS), has several important implications for the properties of biosystems. Among these implications, CISS facilitates long-range electron transfer, enhances bio-affinities and enantioselectivity, and enables efficient and selective multi-electron redox processes. In this article, we review the CISS effect and some of its manifestations in biological systems. We argue that chirality is preserved so persistently in biology not only because of its structural effect, but also because of its important function in spin polarizing electrons. [ABSTRACT FROM AUTHOR]

Spin‐dependent conduction and polarization in chiral polymers were studied for polymers organized as self‐assembled monolayers with conduction along the polymer backbone, namely, along its longer axis. Large spin polarization and magnetoresistance effects were observed, showing a clear dependence on the secondary structure of the polymer. The results indicate that the spin polarization process does not include spin flipping and hence it results from backscattering probabilities for the two spin states. [ABSTRACT FROM AUTHOR]

We show that enantioselective reactions can be induced by the electron spin itself and that it is possible to replace a conventional enantiopure chemical reagent by spin‐polarized electrons that provide the chiral bias for enantioselective reactions. Three examples of enantioselective chemistry resulting from electron‐spin polarization are presented. One demonstrates the enantioselective association of a chiral molecule with an achiral self‐assembled monolayer film that is spin‐polarized, while the other two show that the chiral bias provided by the electron helicity can drive both reduction and oxidation in enantiospecific electrochemical reactions. In each case, the enantioselectivity does not result from enantiospecific interactions of the molecule with the ferromagnetic electrode but from the polarized spin that crosses the interface between the substrate and the molecule. Furthermore, the direction of the electron‐spin polarization defines the handedness of the enantioselectivity. This work demonstrates a new mechanism for realizing enantioselective chemistry. [ABSTRACT FROM AUTHOR]

Electron spin states play an important role in many chemical processes. Most spin-state studies require the application of a magnetic field. Recently it was found that the transport of electrons through chiral molecules also depends on their spin states and may also play a role in enantiorecognition. Electrochemistry is an important tool for studying spin-specific processes and enantioseparation of chiral molecules. A new device is presented, which serves as the working electrode in electrochemical cells and is capable of providing information on the correlation of spin selectivity and the electrochemical process. The device is based on the Hall effect and it eliminates the need to apply an external magnetic field. Spin-selective electron transfer through chiral molecules can be monitored and the relationship between the enantiorecognition process and the spin of electrons elucidated. [ABSTRACT FROM AUTHOR]

The recently discovered chiral induced spin selectivity (CISS) effect gives rise to a spin selective electron transmission through biomolecules. Here we review the mechanism behind the CISS effect and its implication for processes in Biology. Specifically, three processes are discussed: long-range electron transfer, spin effects on the oxidation of water, and enantioselectivity in bio-recognition events. These phenomena imply that chirality and spin may play several important roles in biology, which have not been considered so far. [ABSTRACT FROM AUTHOR]

The search to understand the origin of homochirality in nature has been ongoing since the time of Pasteur. Previous work has shown that DNA can act as a spin filter for low-energy electrons and that spin-polarized secondary electrons produced by X-ray irradiation of a magnetic substrate can induce chiral selective chemistry. In the present work it is demonstrated that secondary electrons from a substrate that are transmitted through a chiral overlayer cause enantiomeric selective chemistry in an adsorbed adlayer. We determine the quantum yields (QYs) for dissociation of ( R)- or ( S)-epichlorohydrin adsorbed on a chiral self-assembled layer of DNA on gold and on bare gold (for control). The results show that there is a significant difference in the QYs between the two enantiomers when adsorbed on DNA, but none when they are adsorbed on bare Au. We propose that the effect results from natural spin filtering effects cause by the chiral monolayer. [ABSTRACT FROM AUTHOR]

Recent experiments have demonstrated that the electron transmission yield through chiral molecules depends on the electron spin orientation. This phenomenon has been termed the chiral-induced spin selectivity (CISS) effect, and it provides a challenge to theory and promise for organic molecule-based spintronic devices. This article reviews recent developments in our understanding of CISS. Different theoretical models have been used to describe the effect; however, they all presume an unusually large spin-orbit coupling in chiral molecules for the effect to display the magnitudes seen in experiments. A simplified model for an electron's transport through a chiral potential suggests that these large couplings can be manifested. Techniques for measuring spin-selective electron transport through molecules are overviewed, and some examples of recent experiments are described. Finally, we present results obtained by studying several systems, and we describe the possible application of the CISS effect for memory devices. [ABSTRACT FROM AUTHOR]

Photosystem I (PSI) is one of the most studied electron transfer (ET) systems in nature; it is found in plants, algae, and bacteria. The effect of the system structure and its electronic properties on the electron transfer rate and yield was investigated for years in details. In this work we show that not only those system properties affect the ET efficiency, but also the electrons' spin. Using a newly developed spintronic device and a technique which enables control over the orientation of the PSI monolayer relative to the device (silver) surface, it was possible to evaluate the degree and direction of the spin polarization in ET in PSI. We find high-spin selectivity throughout the entire ET path and establish that the spins of the electrons being transferred are aligned parallel to their momenta. The spin selectivity peaks at 300 K and vanishes at temperatures below about 150 K. A mechanism is suggested in which the chiral structure of the protein complex plays an important role in determining the high-spin selectivity and its temperature dependence. Our observation of high light induced spin dependent ET in PSI introduces the possibility that spin may play an important role in ET in biology. [ABSTRACT FROM AUTHOR]

Spin-dependent photoelectron transmission and spin-dependent electrochemical studies were conducted on purple membrane containing bacteriorhodopsin (bR) deposited on gold, aluminum/aluminum-oxide, and nickel substrates. The result indicates spin selectivity in electron transmission through the membrane. Although the chiral bR occupies only about 10% of the volume of the membrane, the spin polarization found is on the order of 15%. The electrochemical studies indicate a strong dependence of the conduction on the protein's structure. Denaturation of the protein causes a sharp drop in the conduction through the membrane. [ABSTRACT FROM AUTHOR]

The oxygen reduction efficiency of a laccase-modified electrode was found to depend on the chirality of the oligopeptide linker used to bind the enzyme to the surface. At the same time, the electron transfer between the cathode electrode and the enzyme is improved by using a copper(II) complex with amino-acid derivative Schiff base ligand with/without azobenzene moiety as a mediator. The increased electrochemical current under both O2 and N2 proves that both the mediators are active towards the enzyme. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Conspectus: Molecular spintronics (spin + electronics), which aims to exploit both the spin degree of freedom and the electron charge in molecular devices, has recently received massive attention. Our recent experiments on molecular spintronics employ chiral molecules which have the unexpected property of acting as spin filters, by way of an effect we call “chiral-induced spin selectivity” (CISS). In this Account, we discuss new types of spin-dependent electrochemistry measurements and their use to probe the spin-dependent charge transport properties of nonmagnetic chiral conductive polymers and biomolecules, such as oligopeptides, L/D cysteine, cytochrome c, bacteriorhodopsin (bR), and oligopeptide-CdSe nanoparticles (NPs) hybrid structures. Spin-dependent electrochemical measurements were carried out by employing ferromagnetic electrodes modified with chiral molecules used as the working electrode. Redox probes were used either in solution or when directly attached to the ferromagnetic electrodes. During the electrochemical measurements, the ferromagnetic electrode was magnetized either with its magnetic moment pointing “UP” or “DOWN” using a permanent magnet (H = 0.5 T), placed underneath the chemically modified ferromagnetic electrodes. The spin polarization of the current was found to be in the range of 5–30%, even in the case of small chiral molecules. Chiral films of the l- and d-cysteine tethered with a redox-active dye, toludin blue O, show spin polarizarion that depends on the chirality. Because the nickel electrodes are susceptible to corrosion, we explored the effect of coating them with a thin gold overlayer. The effect of the gold layer on the spin polarization of the electrons ejected from the electrode was investigated. In addition, the role of the structure of the protein on the spin selective transport was also studied as a function of bias voltage and the effect of protein denaturation was revealed. In addition to “dark” measurements, we also describe photoelectrochemical measurements in which light is used to affect the spin selective electron transport through the chiral molecules. We describe how the excitation of a chromophore (such as CdSe nanoparticles), which is attached to a chiral working electrode, can flip the preferred spin orientation of the photocurrent, when measured under the identical conditions. Thus, chirality-induced spin polarization, when combined with light and magnetic field effects, opens new avenues for the study of the spin transport properties of chiral molecules and biomolecules and for creating new types of spintronic devices in which light and molecular chirality provide new functions and properties. [ABSTRACT FROM AUTHOR]

The role of the electron spin in chemistry and biologyhas received much attention recently owing to to the possible electromagneticfield effects on living organisms and the prospect of using moleculesin the emerging field of spintronics. Recently the chiral-inducedspin selectivity effect was observed by electron transmission throughorganic molecules. In the present study, we demonstrated the abilityto control the spin filtering of electrons by light transmitted throughpurple membranes containing bacteriorhodopsin (bR) and its D96N mutant.The spin-dependent electrochemical cyclic voltammetry (CV) and chronoamperometricmeasurements were performed with the membranes deposited on nickelsubstrates. High spin-dependent electron transmission through themembranes was observed; however, after the samples were illuminatedby 532 nm light, the spin filtering in the D96N mutant was dramaticallyreduced whereas the light did not have any effect on the wild-typebR. Beyond demonstrating spin-dependent electron transmission, thiswork also provides an interesting insight into the relationship betweenthe structure of proteins and spin filtering by conducting electrons. [ABSTRACT FROM AUTHOR]

We investigated the effect of anelectric field on the alignment and structural properties of thinfilms of a chiral polybithiophene-based conductive polymer, functionalizedwith a protected l-cysteine amino acid. Thin films were obtainedby exploiting both drop-casting and spin-coating procedures. The electricproperties, the polarized Raman spectrum, the UV–vis spectrum,and the CD spectra were measured as a function of the electric fieldintensity applied during film formation. It was found that beyondthe enhancement of the conductivity observed when the electric fieldaligns the polymer, the electric field significantly affects the chiralproperties and the effect depends on the method of deposition. [ABSTRACT FROM AUTHOR]