Enantiospecificity of Cysteine Adsorption on a Ferromagnetic Surface: Is It Kinetically or Thermodynamically Controlled?

This work uses electrochemical quartz crystal microbalance methods to demonstrate the enantiospecific interaction between a magnetized surface and a chiral amino acid. The enantiospecific adsorption of chiral molecules (cysteine is used as a model) on a ferromagnetic surface is shown to arise from the kinetics of adsorption and not from a thermodynamic stabilization. Measurements of the Gibbs free energy of adsorption for different chiral forms of cysteine and different electrode magnetization states show no significant differences, whereas measurements of the adsorption and desorption kinetics reveal a strong dependence on the magnetization state of the electrode surface. In addition, the enantioselectivity is shown to depend sensitively on the solution pH and the charge state of the chiral adsorbate.

Optical Multilevel Spin Bit Device Using Chiral Quantum Dots.

The technological advancement of data storage is reliant upon the continuous development of faster and denser memory with low power consumption. Recent progress in flash memory has focused on increasing the number of bits per cell to increase information density. In this work an optical multilevel spin bit, based on the chiral induced spin selectivity (CISS) effect, is developed using nanometer sized chiral quantum dots. A double quantum dot architecture is adsorbed on the active area of a Ni based Hall sensor and a nine-state readout is achieved.

Asymmetric reactions induced by electron spin polarization.

Essential aspects of the chiral induced spin selectivity (CISS) effect and their implications for spin-controlled chemistry and asymmetric electrochemical reactions are described. The generation of oxygen through electrolysis is discussed as an example in which chirality-based spin-filtering and spin selection rules can be used to improve the reaction's efficiency and selectivity. Next the discussion shifts to illustrate how the spin selectivity of chiral molecules (CISS properties) allows one to use the electron spin as a chiral bias for inducing asymmetric reactions and promoting enantiospecific processes. Two enantioselective electrochemical reactions that have used polarized electron spins as a chiral reagent are described; enantioselective electroreduction to resolve an enantiomer from a racemic mixture and an oxidative electropolymerization to generate a chiral polymer from achiral monomers. A complementary approach that has used spin-polarized, but otherwise achiral, molecular films to enantiospecifically associate with one enantiomer from a racemic mixture is also discussed. Each of these reaction types use magnetized films to generate the spin polarized electrons and the enantiospecificity can be selected by choice of the magnetization direction, North pole versus South pole. Possible paths for future research in this area and its compatibility with existing methods based on chiral electrodes are discussed.

Chiral Molecules and the Spin Selectivity Effect.

This Perspective discusses recent experiments that bear on the chiral induced spin selectivity (CISS) mechanism and its manifestation in electronic and magnetic properties of chiral molecules and materials. Although the discussion emphasizes newer experiments, such as the magnetization dependence of chiral molecule interactions with ferromagnetic surfaces, early experiments, which reveal the nonlinear scaling of the spin filtering with applied potential, are described also. In many of the theoretical studies, one has had to invoke unusually large spin-orbit couplings in order to reproduce the large spin filtering observed in experiments. Experiments imply that exchange interactions and Pauli exclusion constraints are an important aspect of CISS. They also demonstrate the spin-dependent charge flow between a ferromagnetic substrate and chiral molecules. With these insights in mind, a simplified model is described in which the chiral molecule's spin polarization is enhanced by a spin blockade effect to generate large spin filtering.

Through-Solvent Tunneling in Donor-Bridge-Acceptor Molecules Containing a Molecular Cleft.

Photoinduced electron transfer is used to investigate the solvent-mediated electron tunneling between electron donor and acceptor groups in polar solvents. Bis-peptide scaffolds are used to control the spatial positioning of electron donor and acceptor groups and create a molecular cleft. The photoinduced electron transfer is studied for two different cleft sizes, and the electronic coupling is found to be controlled by the nature of the solvent and the ability of the molecular cleft to accommodate it, as well as interact directly with it. These studies demonstrate the importance of electron tunneling through nonbonded contacts and reveal a strategy for examining such tunneling pathways in polar solvents.

Driving charge separation for hybrid solar cells: photo-induced hole transfer in conjugated copolymer and semiconductor nanoparticle assemblies.

This work reports on the use of an internal electrostatic field to facilitate charge separation at inorganic-organic interfaces, analogous to those in hybrid solar cells. Systematic charge transfer studies show that the donor-acceptor charge transfer rate is highly sensitive to the direction of the internal electric field.

On the electron transfer mechanism between cytochrome C and metal electrodes. Evidence for dynamic control at short distances.

Cytochrome c was coordinatively bound to self-assembled monolayers of pyridine-terminated alkanethiols on Au and Ag electrodes. The mechanism of heterogeneous electron transfer of the immobilized protein was investigated by cyclic voltammetry and time-resolved surface-enhanced resonance Raman spectroelectrochemistry. The temperature, distance, and overpotential dependencies of the electron transfer rates indicate a change of mechanism from a tunneling controlled reaction at long distances (thicker films) to a solvent/protein friction controlled reaction at smaller distances (thinner films).

Molecular chirality and charge transfer through self-assembled scaffold monolayers.

The effect of molecular chirality on electron transmission is explored by photoelectrochemistry. Thiol-terminated chiral scaffold molecules containing a porphyrin chromophore were self-assembled on gold surfaces to form a monolayer. Incorporation of the SAM-coated gold into an electrochemical cell and illumination with visible light generated a cathodic photocurrent. When using circularly polarized light, the photocurrent displayed an asymmetry (different magnitude of photocurrent for right versus left polarization) that changed with the molecular chirality (left- or right-handedness of the scaffold). A symmetry constraint on the electronic coupling between the porphyrin and the organic scaffold is proposed as a possible mechanism for the photocurrent asymmetry.

Fluorescence quenching mechanism of a polyphenylene polyelectrolyte with other macromolecules: cytochrome c and dendrimers.

This study investigates the fluorescence quenching of a polyphenyl based polyelectrolyte by positively charged macromolecules (proteins and dendrimers). This work shows that the fluorescence quenching of the dendrimer materials does not involve energy transfer or electron transfer but is correlated to the overall charge on the dendrimer and its size. The quenching is hypothesized to result from conformational changes that occur upon binding the polyelectrolyte to the protein or dendrimer. This mechanism is qualitatively different from that invoked for small-molecule analytes.

Organization-induced charge redistribution in self-assembled organic monolayers on gold.

The charge redistribution that occurs within dipolar molecules as they self-assemble into organized organic monolayer films has been studied. The extent of charge transfer is probed by work function measurements, using low-energy photoelectron spectroscopy (LEPS), contact potential difference (CPD), and X-ray photoelectron spectroscopy (XPS), with the latter providing fine details about the internal charge distribution along the molecule. In addition, two-photon photoelectron spectroscopy is applied to investigate the electronic structure of the adsorbed layers. We show that charge transfer acts to reduce the dipole-dipole interaction between the molecules but may either decrease or increase the molecule-to-surface dipole moment.

The dependence of electron transfer efficiency on the conformational order in organic monolayers.

The electron transfer through an organized organic monolayer of alkyl chains adsorbed on a silicon wafer has been studied. The silicon was used as an electrode in a three-electrode electrochemical cell, and the current versus voltage response was measured. The results show that when the chains in the monolayer are in the "all trans" configuration, the charge transfer efficiency is higher than when the chains have a "gauche" configuration. A mechanism rationalizing all the observations is suggested.