Vibration induced memory effects and switching in ac-driven molecular nanojunctions

We investigate bistability and memory effects in a molecular junction weakly coupled to metallic leads with the latter being subject to an adiabatic periodic change of the bias voltage. The system is described by a simple Anderson-Holstein model and its dynamics is calculated via a master equation approach. The controlled electrical switching between the many-body states of the system is achieved due to polaron shift and Franck-Condon blockade in the presence of strong electron-vibron interaction. Particular emphasis is given to the role played by the excited vibronic states in the bistability and hysteretic switching dynamics as a function of the voltage sweeping rates. In general, both the occupation probabilities of the vibronic states and the associated vibron energy show hysteretic behaviour for driving frequencies in a range set by the minimum and maximum lifetimes of the system. The consequences on the transport properties for various driving frequencies and in the limit of DC-bias are also investigated.     

Correlated tunneling in intramolecular carbon nanotube quantum dots

We investigate correlated electronic transport in single-walled carbon nanotubes with two intramolecular tunneling barriers. We suggest that below a characteristic temperature the long-range nature of the Coulomb interaction becomes crucial to determine the temperature dependence of the maximum G(max) of the conductance peak. Correlated sequential tunneling dominates transport yielding the power law G(max) proportional, variant T(alpha(end-end)-1), typical for tunneling between the ends of two Luttinger liquids. Our predictions are in agreement with recent measurements.     

Application of high-resolution magic-angle spinning NMR spectroscopy to define the cell uptake of MRI contrast agents

A new method, based on proton high-resolution magic-angle spinning ((1)H HR-MAS) NMR spectroscopy, has been employed to study the cell uptake of magnetic resonance imaging contrast agents (MRI-CAs). The method was tested on human red blood cells (HRBC) and white blood cells (HWBC) by using three gadolinium complexes, widely used in diagnostics, Gd-BOPTA, Gd-DTPA, and Gd-DOTA, and the analogous complexes obtained by replacing Gd(III) with Dy(III), Nd(III), and Tb(III) (i.e., complexes isostructural to the ones of gadolinium but acting as shift agents). The method is based on the evaluation of the magnetic effects, line broadening, or induced lanthanide shift (LIS) caused by these complexes on NMR signals of intra- and extracellular water. Since magnetic effects are directly linked to permeability, this method is direct. In all the tests, these magnetic effects were detected for the extracellular water signal only, providing a direct proof that these complexes are not able to cross the cell membrane. Line broadening effects (i.e., the use of gadolinium complexes) only allow qualitative evaluations. On the contrary, LIS effects can be measured with high precision and they can be related to the concentration of the paramagnetic species in the cellular compartments. This is possible because the HR-MAS technique provides the complete elimination of bulk magnetic susceptibility (BMS) shift and the differentiation of extra- and intracellular water signals. Thus with this method, the rapid quantification of the MRI-CA amount inside and outside the cells is actually feasible.     

Spectroscopy of a driven solid-state qubit coupled to a structured environment

We study the asymptotic dynamics of a driven spin-boson system where the environment is formed by a broadened localized mode. Upon exploiting an exact mapping, an equivalent formulation of the problem in terms of a quantum two-state system (qubit) coupled to a harmonic oscillator which is itself Ohmically damped, is found. We calculate the asymptotic population difference of the two states in two complementary parameter regimes. For weak damping and low temperature, a perturbative Floquet-Born-Markovian master equation for the qubit-oscillator system can be solved. We find multi-photon resonances corresponding to transitions in the coupled quantum system and calculate their line-shape analytically. In the complementary parameter regime of strong damping and/or high temperatures, non-perturbative real-time path integral techniques yield analytic results for the resonance line shape. In both regimes, we find very good agreement with exact results obtained from a numerical real-time path-integral approach. Finally, we show for the case of strong detuning between qubit and oscillator that the width of the n-photon resonance scales with the nth Bessel function of the driving strength in the weak-damping regime.     

Quantum ratchet effect for vortices

We have measured a quantum ratchet effect for vortices moving in a quasi-one-dimensional Josephson junction array. In this solid-state device the shape of the vortex potential energy, and consequently the band structure, can be accurately designed. This band structure determines the presence or absence of the quantum ratchet effect. In particular, asymmetric structures possessing only one band below the barrier do not exhibit current rectification at low temperatures and bias currents. The quantum nature of transport is also revealed in a universal/nonuniversal power-law dependence of the measured voltage-current characteristics for samples without/with rectification.     

Strong coupling theory for driven tunneling and vibrational relaxation

We investigate on a unified basis tunneling and vibrational relaxation in driven dissipative multistable systems described by their N lowest lying unperturbed levels. By use of the discrete variable representation we derive a set of coupled non-Markovian master equations. We present analytical treatments that describe the dynamics in the regime of strong system-bath coupling. Our findings are corroborated by "ab initio" real-time path integral calculations.     

Covalent selection of the thiol proteome on activated thiol sepharose: A robust tool for redox proteomics

Protein thiols contribute significantly to antioxidant defence and selective oxidation of cysteines is important in signal transduction even in sub-stress scenarios. However, cysteine is the second rarest residue in proteins and it can be difficult to target low-abundance thiol (-SH)-containing proteins in proteomic separations. Activated thiol sepharose (ATS) allows covalent selection of -SH-containing proteins which can then be recovered by reduction with mercaptoethanol or dithiothreitol. This is a robust method for enriching -SH-containing proteins. We have used ATS to estimate the percentage (by weight) of thiol-containing proteins in cell extracts from a range of biological sources: a bacterium, Escherichia coli; a fungus, Trichoderma harzianum; and a bivalve mollusc Mytilus edulis. -SH-containing proteins account for 2.52% (E. coli), 1.4% (T. harzianum) and 1.4% (M. edulis) of total protein. Exposure to pro-oxidants did not materially alter these values. On removal of low M_r thiols such as glutathione, the values for M. edulis did not significantly change but those for T. harzianum increased threefold. The two-dimensional electrophoresis profiles of ATS-selected proteins for each organism were compared in control and pro-oxidant-exposed preparations. This revealed that some proteins present in controls were absent in pro-oxidant-treated extracts which we attribute to thiol oxidation. ATS has significant potential in enrichment for -SH-containing proteins in redox proteomics.     

Tereoselective total synthesis of racemic grandisol : An improved convenient procedure

(±) Grandisol has been stereoselectively synthesized in a 31% overall yield by a practical and convenient procedure employing the Salomon photobicyclization as the key-step.