Giant orbital magnetic moments and paramagnetic shift in artificial relativistic atoms and molecules.

Materials such as graphene and topological insulators host massless Dirac fermions that enable the study of relativistic quantum phenomena. Single quantum dots and coupled quantum dots formed with massless Dirac fermions can be viewed as artificial relativistic atoms and molecules, respectively. Such structures offer a unique testbed to study atomic and molecular physics in the ultrarelativistic regime (particle speed close to the speed of light). Here we use a scanning tunnelling microscope to create and probe single and coupled electrostatically defined graphene quantum dots to unravel the magnetic-field responses of artificial relativistic nanostructures. We observe a giant orbital Zeeman splitting and orbital magnetic moment up to ~70 meV T-1 and ~600µB (µB, Bohr magneton) in single graphene quantum dots. For coupled graphene quantum dots, Aharonov-Bohm oscillations and a strong Van Vleck paramagnetic shift of ~20 meV T-2 are observed. Our findings provide fundamental insights into relativistic quantum dot states, which can be potentially leveraged for use in quantum information science.

Subterahertz spin pumping from an insulating antiferromagnet.

Spin-transfer torque and spin Hall effects combined with their reciprocal phenomena, spin pumping and inverse spin Hall effects (ISHEs), enable the reading and control of magnetic moments in spintronics. The direct observation of these effects remains elusive in antiferromagnetic-based devices. We report subterahertz spin pumping at the interface of the uniaxial insulating antiferromagnet manganese difluoride and platinum. The measured ISHE voltage arising from spin-charge conversion in the platinum layer depends on the chirality of the dynamical modes of the antiferromagnet, which is selectively excited and modulated by the handedness of the circularly polarized subterahertz irradiation. Our results open the door to the controlled generation of coherent, pure spin currents at terahertz frequencies.

Protein bioelectronics: a review of what we do and do not know.

We review the status of protein-based molecular electronics. First, we define and discuss fundamental concepts of electron transfer and transport in and across proteins and proposed mechanisms for these processes. We then describe the immobilization of proteins to solid-state surfaces in both nanoscale and macroscopic approaches, and highlight how different methodologies can alter protein electronic properties. Because immobilizing proteins while retaining biological activity is crucial to the successful development of bioelectronic devices, we discuss this process at length. We briefly discuss computational predictions and their connection to experimental results. We then summarize how the biological activity of immobilized proteins is beneficial for bioelectronic devices, and how conductance measurements can shed light on protein properties. Finally, we consider how the research to date could influence the development of future bioelectronic devices.

Room temperature ferroelectricity in fluoroperovskite thin films.

The NaMnF3 fluoride-perovskite has been found, theoretically, to be ferroelectric under epitaxial strain becoming a promising alternative to conventional oxides for multiferroic applications. Nevertheless, this fluoroperovskite has not been experimentally verified to be ferroelectric so far. Here we report signatures of room temperature ferroelectricity observed in perovskite NaMnF3 thin films grown on SrTiO3. Using piezoresponse force microscopy, we studied the evolution of ferroelectric polarization in response to external and built-in electric fields. Density functional theory calculations were also performed to help understand the strong competition between ferroelectric and paraelectric phases as well as the profound influences of strain. These results, together with the magnetic order previously reported in the same material, pave the way to future multiferroic and magnetoelectric investigations in fluoroperovskites.

Identification of photocurrents in topological insulators.

Optical injection and detection of charge currents is an alternative to conventional transport and photoemission measurements, avoiding the necessity of invasive contact that may disturb the system being examined. This is a particular concern for analyzing the surface states of topological insulators. In this work one- and two-color sources of photocurrents are isolated and examined in epitaxial thin films of Bi2Se3. We demonstrate that optical excitation and terahertz detection simultaneously captures one- and two-color photocurrent contributions, which has not been required for other material systems. A method is devised to extract the two components, and in doing so each can be related to surface or bulk excitations through symmetry. The separation of such photocurrents in topological insulators opens a new avenue for studying these materials by all-optical methods.

Nonlinear optical observation of coherent acoustic Dirac plasmons in thin-film topological insulators.

Low-energy collective electronic excitations exhibiting sound-like linear dispersion have been intensively studied both experimentally and theoretically for a long time. However, coherent acoustic plasmon modes appearing in time-domain measurements are rarely observed due to Landau damping by the single-particle continua. Here we report on the observation of coherent acoustic Dirac plasmon (CADP) modes excited in indirectly (electrostatically) opposite-surface coupled films of the topological insulator Bi2Se3. Using transient second-harmonic generation, a technique capable of independently monitoring the in-plane and out-of-plane electron dynamics in the films, the GHz-range oscillations were observed without corresponding oscillations in the transient reflectivity. These oscillations were assigned to the transverse magnetic and transverse electric guided CADP modes induced by the evanescent guided Lamb acoustic waves and remained Landau undamped due to fermion tunnelling between the opposite-surface Dirac states.

Effect of Mn doping on ultrafast carrier dynamics in thin films of the topological insulator Bi2Se3.

Transient reflectivity (TR) measured at laser photon energy 1.51 eV from the indirectly intersurface-coupled topological insulator Bi2-x Mn x Se3 films (12 nm thick) revealed a strong dependence of the rise-time and initial decay-time constants on photoexcited carrier density and Mn content. In undoped samples (x = 0), these time constants are exclusively governed by electron-electron and electron-phonon scattering, respectively, whereas in films with x = 0.013-0.27 ultrafast carrier dynamics are completely controlled by photoexcited electron trapping by ionized Mn(2+) acceptors and their dimers. The shortest decay-time (~0.75 ps) measured for the film with x = 0.27 suggests a great potential of Mn-doped Bi2Se3 films for applications in high-speed optoelectronic devices. Using Raman spectroscopy exploiting similar laser photon energy (1.58 eV), we demonstrate that due to indirect intersurface coupling in the films, the photoexcited electron trapping in the bulk enhances the electron-phonon interaction strength in Dirac surface states.

Antiferromagnetic Spin Seebeck Effect.

We report on the observation of the spin Seebeck effect in antiferromagnetic MnF_{2}. A device scale on-chip heater is deposited on a bilayer of MnF_{2} (110) (30 nm)/Pt (4 nm) grown by molecular beam epitaxy on a MgF_{2} (110) substrate. Using Pt as a spin detector layer, it is possible to measure the thermally generated spin current from MnF_{2} through the inverse spin Hall effect. The low temperature (2-80 K) and high magnetic field (up to 140 kOe) regime is explored. A clear spin-flop transition corresponding to the sudden rotation of antiferromagnetic spins out of the easy axis is observed in the spin Seebeck signal when large magnetic fields (>9 T) are applied parallel to the easy axis of the MnF_{2} thin film. When the magnetic field is applied perpendicular to the easy axis, the spin-flop transition is absent, as expected.

Multiferroic BaCoF4 in Thin Film Form: Ferroelectricity, Magnetic Ordering, and Strain.

Multiferroic materials have simultaneous magnetic and ferroelectric long-range orders and can be potentially useful for a wide range of applications. Conventional ferroelectricity in oxide perovskites favors nonmagnetic electronic configurations of transition metal ions, thus limiting the number of intrinsic multiferroic materials. On the other hand, this is not necessarily true for multiferroic fluorides. Using molecular beam epitaxy, we demonstrate for the first time that the multiferroic orthorhombic fluoride BaCoF4 can be synthesized in thin film form. Ferroelectric hysteresis measurements and piezoresponse force microscopy show that the films are indeed ferroelectric. From structural information, magnetic measurements, and first-principles calculations, a modified magnetic ground state is identified which can be represented as a combination of bulk collinear antiferromagnetism with two additional canted spin orders oriented along orthogonal axes of the BaCoF4 unit cell. The calculations indicate that an anisotropic epitaxial strain is responsible for this unusual magnetic ground state.

Nanoscale electron transport measurements of immobilized cytochrome P450 proteins.

Gold nanopillars, functionalized with an organic self-assembled monolayer, can be used to measure the electrical conductance properties of immobilized proteins without aggregation. Measurements of the conductance of nanopillars with cytochrome P450 2C9 (CYP2C9) proteins using conducting probe atomic force microscopy demonstrate that a correlation exists between the energy barrier height between hopping sites and CYP2C9 metabolic activity. Measurements performed as a function of tip force indicate that, when subjected to a large force, the protein is more stable in the presence of a substrate. This agrees with the hypothesis that substrate entry into the active site helps to stabilize the enzyme. The relative distance between hopping sites also increases with increasing force, possibly because protein functional groups responsible for electron transport (ETp) depend on the structure of the protein. The inhibitor sulfaphenazole, in addition to the previously studied aniline, increased the barrier height for electron transfer and thereby makes CYP2C9 reduction more difficult and inhibits metabolism. This suggests that P450 Type II binders may decrease the ease of ETp processes in the enzyme, in addition to occupying the active site.

Phase diagram of a three-dimensional antiferromagnet with random magnetic anisotropy.

Three-dimensional antiferromagnets with random magnetic anisotropy (RMA) that have been experimentally studied to date have competing two-dimensional and three-dimensional exchange interactions which can obscure the authentic effects of RMA. The magnetic phase diagram of Fe_{x}Ni_{1-x}F_{2} epitaxial thin films with true random single-ion anisotropy was deduced from magnetometry and neutron scattering measurements and analyzed using mean-field theory. Regions with uniaxial, oblique, and easy-plane anisotropies were identified. A RMA-induced glass region was discovered where a Griffiths-like breakdown of long-range spin order occurs.

Thickness tunable quantum interference between surface phonon and Dirac plasmon states in thin films of the topological insulator Bi2Se3.

We report on a >100-fold enhancement of Raman responses from Bi2Se3 thin films if laser photon energy switches from 2.33 eV (532 nm) to 1.58 eV (785 nm), which is due to direct optical coupling to Dirac surface states (SS) at the resonance energy of ∼1.5 eV (a thickness-independent enhancement) and due to nonlinearly excited Dirac plasmon (a thickness-dependent enhancement). Owing to the direct optical coupling, we observed an in-plane phonon mode of hexagonally arranged Se-atoms associated with a continuous network of Dirac SS. This mode revealed a Fano lineshape for films <15 nm thick, resulting from quantum interference between surface phonon and Dirac plasmon states.

Measurement of electron transfer through cytochrome P450 protein on nanopillars and the effect of bound substrates.

Electron transfer in cytochrome P450 enzymes is a fundamental process for activity. It is difficult to measure electron transfer in these enzymes because under the conditions typically used they exist in a variety of states. Using nanotechnology-based techniques, gold conducting nanopillars were constructed in an indexed array. The P450 enzyme CYP2C9 was attached to each of these nanopillars, and conductivity measurements made using conducting probe atomic force microscopy under constant force conditions. The conductivity measurements were made on CYP2C9 alone and with bound substrates, a bound substrate-effector pair, and a bound inhibitor. Fitting of the data with the Poole-Frenkel model indicates a correlation between the barrier height for electron transfer and the ease of CYP2C9-mediated metabolism of the bound substrates, though the spin state of iron is not well correlated. The approach described here should have broad application to the measurement of electron transfer in P450 enzymes and other metalloenzymes.

An investigation into the feasibility of myoglobin-based single-electron transistors.

Myoglobin single-electron transistors were investigated using nanometer-gap platinum electrodes fabricated by electromigration at cryogenic temperatures. Apomyoglobin (myoglobin without the heme group) was used as a reference. The results suggest single-electron transport is mediated by resonant tunneling with the electronic and vibrational levels of the heme group in a single protein. They also represent a proof-of-principle that proteins with redox centers across nanometer-gap electrodes can be utilized to fabricate single-electron transistors. The protein orientation and conformation may significantly affect the conductance of these devices. Future improvements in device reproducibility and yield will require control of these factors.

Interface biquadratic coupling and magnon scattering in exchange-biased ferromagnetic thin films grown on epitaxial FeF2.

The magnetic anisotropy of ferromagnetic (FM) Ni, Co, and Fe polycrystalline thin films grown on antiferromagnetic (AF) FeF(2)(110) epitaxial layers was studied, as a function of temperature, using ferromagnetic resonance. In addition to an in-plane anisotropy in the FM induced by fluctuations in the AF short-range order, a perpendicular (biquadratic) magnetic anisotropy, with an out-of-plane component, was found which increased with decreasing temperature above the AF Neél temperature (T(N) = 78.4 K). This is a surprising result given that the AF's uniaxial anisotropy axis was in the plane of the sample, but is consistent with prior experimental and theoretical work. The resonance linewidth had a strong dependence on the direction of the external magnetic field with respect to in-plane FeF(2) crystallographic directions, consistent with interface magnon scattering due to defect-induced demagnetizing fields. Below T(N), the exchange bias field H(E) measured via FMR for the Ni sample was in good agreement with H(E) determined from magnetization measurements if the perpendicular out-of-plane anisotropy was taken into account. A low field resonance line normally observed at H ≈ 0, associated with domain formation during magnetization in ferromagnets, coincided with the exchange bias field for T < T(N), indicating domain formation with the in-plane FM magnetization perpendicular to the AF easy axis. Thus, biquadratic FM-AF coupling is important at temperatures below and above T(N).

Electrocatalytic drug metabolism by CYP2C9 bonded to a self-assembled monolayer-modified electrode.

Cytochrome P450 (P450) enzymes typically require the presence of at least cytochrome P450 reductase (CPR) and NADPH to carry out the metabolism of xenobiotics. To address whether the need for redox transfer proteins and the NADPH cofactor protein could be obviated, CYP2C9 was bonded to a gold electrode through an 11-mercaptoundecanoic acid and octanethiol self-assembled monolayer (SAM) through which a current could be applied. Cyclic voltammetry demonstrated direct electrochemistry of the CYP2C9 enzyme bonded to the electrode and fast electron transfer between the heme iron and the gold electrode. To determine whether this system could metabolize warfarin analogous to microsomal or expressed enzyme systems containing CYP2C9, warfarin was incubated with the CYP2C9-SAM-gold electrode and a controlled potential was applied. The expected 7-hydroxywarfarin metabolite was observed, analogous to expressed CYP2C9 systems, wherein this is the predominant metabolite. Current-concentration data generated with increasing concentrations of warfarin were used to determine the Michaelis-Menten constant (K(m)) for the hydroxylation of warfarin (3 microM), which is in good agreement with previous literature regarding K(m) values for this reaction. In summary, the CYP2C9-SAM-gold electrode system was able to carry out the metabolism of warfarin only after application of an electrical potential, but in the absence of either CPR or NADPH. Furthermore, this system may provide a unique platform for both studying P450 enzyme electrochemistry and as a bioreactor to produce metabolites without the need for expensive redox transfer proteins and cofactors.

Preparation, characterization, and substrate metabolism of gold-immobilized cytochrome P450 2C9.

The cytochrome P450 enzymes represent an important class of heme-containing enzymes. There is considerable interest in immobilizing these enzymes on a surface so that interactions between a single enzyme and other species can be studied with respect to electron transfer, homodimer or heterodimer interactions, or for construction of biological-based chips for standardizing cytochrome P450 metabolism or for high-throughput screening of pharmaceutical agents. Previous studies have generally immobilized P450 enzymes in a matrix or on a surface. Here, we have attached CYP2C9 to gold substrates such that the resulting construct maintains the ability to bind and metabolize substrates in the presence of NADPH and cytochrome P450 reductase. The activity of these chips is directly dependent upon the linkers used to attach CYP2C9 and to the presence of key molecules in the active site during enzyme attachment. A novel method to detect substrate-enzyme binding, namely, superconducting quantum interference device (SQUID) magnetometry, was used to monitor the binding of substrates. Most significantly, conditions that allow measurable CYP2C9 metabolism to occur have been developed.

Parallel versus antiparallel interfacial coupling in exchange biased Co/FeF2.

By using the surface and element specificity of soft x-ray magnetic dichroism we provide direct experimental evidence for two different types of interfacial uncompensated Fe moments in exchange biased Co/FeF2 bilayers. Some moments are pinned and coupled antiparallel to the ferromagnet (FM). They give rise to a positive exchange bias and vanish above T(N) = 78 together with the antiferromagnet (AF) order. Other interfacial Fe moments are unpinned and coupled parallel to the FM. They persist up to 300 K and give rise to magnetic order at the AF surface even above T(N) .

Reducing morbidity and mortality from oral and oropharyngeal cancer.

There has been no reduction in the incidence of OOPCa, nor has the 5-year survival rate improved over the past 30 years. Most of these cancers are diagnosed in the later stages after they have grown to significant size, have become fixed to surrounding structures, hemorrhagic or painful or have caused noticeable impairment of speech or deglutition. To reduce the incidence of OOPCa and improve outcomes, the public must become more aware of the risk factors and seek regular oral cancer examination. More importantly, health professionals must incorporate a thorough oral soft tissue examination into their routine evaluation of all patients. Although an array of promising new technologies is becoming part of our diagnostic armamentarium, the most important factor is, as it has always been, an educated, astute and conscientious clinician.

Comparison of computer-assisted brush biopsy results with follow up scalpel biopsy and histology.

Oral brush biopsy results were compared with scalpel biopsy and histology to determine the positive predictive value of an abnormal brush biopsy finding. Of 243 patients with abnormal brush biopsies, 93 proved positive for dysplasia (79) or carcinoma (14) and 150 were negative for either dysplasia or carcinoma. Therefore, the positive predictive value of an abnormal brush biopsy was 38% (93/243). By using the oral brush biopsy, dentists can inform their patients that abnormal findings have a strong positive predictive value for dysplasia or carcinoma and therefore require follow-up confirmation by scalpel biopsy.