Tal Z. Markus

Spin Selectivity in Electron Transmission Through Self-Assembled Monolayers of Double-Stranded DNA

Photoelectrons emitted from a DNA-covered gold surface can have an unbalanced spin population of up to 60%. In electron-transfer processes, spin effects normally are seen either in magnetic materials or in systems containing heavy atoms that facilitate spin-orbit coupling. We report spin-selective transmission of electrons through self-assembled monolayers of double-stranded DNA on gold. By directly measuring the spin of the transmitted electrons with a Mott polarimeter, we found spin polarizations exceeding 60% at room temperature. The spin-polarized photoelectrons were observed even when the photoelectrons were generated with unpolarized light. The observed spin selectivity at room temperature was extremely high as compared with other known spin filters. The spin filtration efficiency depended on the length of the DNA in the monolayer and its organization.

Spin Specific Electron Conduction through DNA Oligomers

Spin-based properties, applications, and devices are commonly related to magnetic effects and to magnetic materials. Most of the development in spintronics is currently based on inorganic materials. Despite the fact that the magnetoresistance effect has been observed in organic materials, until now spin selectivity of organic based spintronics devices originated from an inorganic ferromagnetic electrode and was not determined by the organic molecules themselves. Here we show that conduction through double-stranded DNA oligomers is spin selective, demonstrating a true organic spin filter. The selectivity exceeds that of any known system at room temperature. The spin dependent resistivity indicates that the effect cannot result solely from the atomic spin-orbit coupling and must relate to a special property resulting from the chirality symmetry. The results may reflect on the importance of spin in determining electron transfer rates through biological systems.

Chiral imprinting of palladium with cinchona alkaloids.

In the search for new materials and concepts in materials science, metallo-organic hybrids are attractive candidates; they can combine the rich diversity of organic molecules with the advantages of metals. Transition metals such as palladium are widely applied in catalysis, and small organic molecules such as those in the cinchona alkaloid family can control the stereochemistry of a number of organic reactions. Here, we show that reducing a metal salt in the presence of a cinchona alkaloid dopant gives a chirally imprinted metallo-organic hybrid material that is catalytically active and shows moderate enantioselectivity in hydrogenation. Furthermore, using photoelectron emission spectroscopy, we show that the metal retains some chiral character even after extraction of the dopant. This simple and effective methodology opens exciting opportunities for developing a variety of chiral composite materials.

Spin-dependent electron transmission through bacteriorhodopsin embedded in purple membrane

Significance The role of the electron spin in chemistry and biology has been receiving much attention because of a plausible relation to electromagnetic field effects on living organisms. Part of the difficulty in studying the subject arises from the lack of a physical model that can rationalize these phenomena. Recently the chiral-induced spin selectivity effect was observed in electron transmission through organic molecules. The question is to what extent the effect takes place in proteins. In the present study, we probed bacteriorhodopsin embedded in its native membrane environment. We observed clear evidence for spin-dependent electron transmission through this system. The results point to the possibility that the effect may play a role in electron transfer in biological systems. 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.

Electronic structure of DNA-unique properties of 8-oxoguanosine

8-Oxo-7,8-dihydroguanosine (8-oxoG) is among the most common forms of oxidative DNA damage found in human cells. The question of damage recognition by the repair machinery is a long standing one, and it is intriguing to suggest that the mechanism of efficiently locating damage within the entire genome might be related to modulations in the electronic properties of lesions compared to regular bases. Using laser-based methods combined with organizing various oligomers self-assembled monolayers on gold substrates, we show that indeed 8-oxoG has special electronic properties. By using oligomers containing 8-oxoG and guanine bases which were inserted in an all thymine sequences, we were able to determine the energy of the HOMO and LUMO states and the relative density of electronic states below the vacuum level. Specifically, it was found that when 8-oxoG is placed in the oligomer, the HOMO state is at higher energy than in the other oligomers studied. In contrast, the weakly mutagenic 8-oxo-7,8-dihydroadenosine (8-oxoA) has little or no effect on the electronic properties of DNA.

Cooperative Effect in the Electronic Properties of Human Telomere Sequence

The contribution of sequence elements of human telomere DNA to the interaction of DNA with electrons has been analyzed. By applying wavelength dependent low-energy photoelectron transmission and two-photon photoemission spectroscopy, we investigated the density of states of DNA oligomers with partial sequence elements of the human telomere assembled as monolayers on gold. The findings demonstrate the role of the resonance states in the DNA in accepting electrons and the effect of the sequence on these states. When guanine (G) bases are clustered together, the resonance negative ion state is stabilized, as compared to oligomers containing the same number of G bases but distributed within the sequence. The electron-capturing probability of the human telomere-like oligomer, a sequence with an additional single adenine (A) base adjacent to the G cluster, is dramatically enhanced compared to the other oligomers studied, most likely due to the enhancement of the density of states near the highest occupied molecular orbital.

How Isolated Are the Electronic States of the Core in Core/Shell Nanoparticles?

We investigated how isolated are the electronic states of the core in a core-shell (c/s) nanoparticles (NPs) from the surface, when the particles are self-assembled on Au substrates via a dithiol (DT) organic linker. Applying photoemission spectroscopy the electronic states of CdSe core only and CdSe/ZnS c/s NPs were compared. The results indicate that in the c/s NPs the HOMO interacts strongly with electronic states in the Au substrate and is pinned at the same energies, relative to the Fermi level, as the core only NPs. When the capping molecules of the NPs were replaced with thiolated molecules, an interaction between the thiol groups and the electronic states of the NPs was observed that depends on the properties of the NPs studied. Thiols binding to the NPs induce the formation of surface trap states. However, while for the core only CdSe NPs the LUMO states are strongly coupled to the surface traps, independent of their size, this coupling is size dependent in the case of the CdSe/ZnS c/s NPs. For a large core, the LUMO is decoupled from the surface trap states. When the core is small enough, the LUMO is delocalized and interacts with these states.