Spatially dependent Kondo effect in quantum corrals

We study the Kondo screening of a single magnetic impurity inside a nonmagnetic quantum corral located on the surface of a metallic host system. We show that the spatial structure of the corral's eigenmodes leads to a spatially dependent Kondo effect whose signatures are spatial variations of the Kondo temperature T K. Moreover, we predict that the Kondo screening is accompanied by the formation of multiple Kondo resonances with characteristic spatial patterns. Our results open new possibilities to manipulate and explore the Kondo effect by using quantum corrals.     

Atomistic mechanism of boron diffusion in silicon

B diffuses in crystalline Si by reacting with a Si self-interstitial (I) with a frequency g and so forming a fast migrating BI complex that can migrate for an average length lambda. We experimentally demonstrate that both g and lambda strongly depend on the free hole concentration p. At low p, g has a constant trend and lambda increases with p, while at high p, g has a superlinear trend and lambda decreases with p. This demonstrates that BI forms in the two regimes by interaction with neutral and double positive I, respectively, and its charge state has to change by interaction with free holes before diffusing.     

Nonvolatile gate effect in a ferroelectric-semiconductor quantum well

Field effect transistors with ferroelectric gates would make ideal rewritable nonvolatile memories were it not for the severe problems in integrating the ferroelectric oxide directly on the semiconductor channel. We propose a powerful way to avoid these problems using a gate material that is ferroelectric and semiconducting simultaneously. First, ferroelectricity in semiconductor (Cd,Zn)Te films is proven and studied using modified piezoforce scanning probe microscopy. Then, a rewritable field effect device is demonstrated by local poling of the (Cd,Zn)Te layer of a (Cd,Zn)Te/CdTe quantum well, provoking a reversible, nonvolatile change in the resistance of the 2D electron gas. The results point to a potential new family of nanoscale one-transistor memories.     

Role of elastic stress in statistical and scaling properties of elastic turbulence

The role of elastic stress in statistical and scaling properties of elastic turbulence in a polymer solution flow between two disks is discussed. The analogy with a small-scale magnetodynamics and a passive scalar turbulent advection in the Batchelor regime is used to explain the experimentally observed statistical properties, the flow structure, and the scaling of elastic turbulence. The emergence of a new length scale, namely, the boundary layer thickness, is observed and studied.     

Nucleotide recognition and phosphate linkage hydrolysis at a lipid cubic interface

Mononucleotides, when entrapped within a mono-olein-based cubic Ia3d liquid crystalline phase, have been found to undergo hydrolysis at the sugar-phosphate ester bond in spite of their natural inertness toward hydrolysis. Here, kinetics of the hydrolysis reaction and interactions between the lipid matrix and the mononucleotide adenosine 5'-monophosphate disodium salt (AMP) and its 2'-deoxy derivative (dAMP) are thoroughly investigated in order to shed some light on the mechanism of the nucleotide recognition and phosphate ester hydrolysis. Experiments evidenced that molecular recognition occurs essentially through the sn-2 and the sn-3 alcoholic OH groups of mono-olein. As deduced from the apparent activation energies, the mechanism underlying the hydrolysis reaction is the same for AMP and dAMP. Nevertheless, the reaction proceeds slower for the latter, highlighting a substantial difference in the chemical behavior of the two nucleotides. A model that explains the hydrolysis reaction is presented. Remarkably, the hydrolysis mechanism appears to be highly specific for the Ia3d phase.     

Amyloid fibril polymorphism is under kinetic control

Self-assembly of proteins into amyloid aggregates displays a broad diversity of morphologies, both at the protofibrillar and final fibrillar species. These polymorphic species can coexist at fixed experimental conditions, and their relative abundance can be controlled by changing the solvent composition, or stirring the solution. However, the extent to which external conditions regulate the equilibrium of morphologically distinct species is still unknown. Here we investigate the nucleation of distinct fibril morphologies using computer simulations of a simplified model of an amyloid polypeptide. Counterintuitively, the energetically less favorable fibril morphologies nucleate more frequently than the morphologies of higher stability for models with low aggregation propensity. The free-energy profiles of the aggregation process indicate that the nucleation barrier determines the population fractions of different fibril morphologies, i.e., amyloid polymorphism is under kinetic control.     

Investigations into bis(triphenylphosphine)copper(I) complexes with cyclic derivatives of methylpyruvate thiosemicarbazones

The syntheses of four compounds, obtained by the reaction of methylpyruvate thiosemicarbazone (Hmpt) and its methyl (Me-Hmpt) and allyl (Allyl-Hmpt) derivatives with bis(triphenylphosphine)copper(I) acetate, are reported. The compounds [Cu(PPh₃)₂(pt_c)(Hpt_c)]·H₂O (1), [Cu(PPh₃)₂(Me-pt_c)] (2), [Cu₂(PPh₃)₂μ-S(Me-pt)μ-S(Me-pt_c)]·H₂O (3) and [Cu(PPh₃)₂(Allyl-pt_c)] (4) [H₂pt = pyruvic acid thiosemicarbazone and Hpt_c = cyclized pyruvic acid thiosemicarbazone, Me = methyl and Allyl are radical substituents on the amino nitrogen] were characterized by elemental analysis, IR, ¹H NMR, and by X-ray crystallography. Compound 3 was also studied by EPR because of the presence in the compound of two copper atoms in two different oxidation states. During the complexation reaction, the thiosemicarbazone ligands tend to undergo a cyclization reaction that leads to the formation of a six-member heterocyclic ring. All four compounds present the [Cu(PPh₃)₂]⁺ fragment and constant but different coordination situations. Compound 1 contains two cyclic ligand molecules, one protonated and the other deprotonated, bound as monodentate through the sulfur. Compounds 2 and 4 present a single deprotonated cyclic SN bidentate ligand molecule, while compound 3 contains copper(I) and copper(II), and two ligand molecules, one of which is linear and behaves as SNO tridentate and the other is cyclic and behaves as bridging μSN.     

3D Particle Tracking on a Two-Photon Microscope

A 3D single-particle-tracking (SPT) system was developed based on two-photon excitation fluorescence microscopy that can track the motion of particles in three dimensions over a range of 100 μm and with a bandwidth up to 30 Hz. We have implemented two different techniques employing feedback control. The first technique scans a small volume around a particle to build up a volumetric image that is then used to determine the particle's position. The second technique scans only a single plane but utilizes optical aberrations that have been introduced into the optical system that break the axial symmetry of the point spread function and serve as an indicator of the particle's axial position. We verified the performance of the instrument by tracking particles in well-characterized models systems. We then studied the 3D viscoelastic mechanical response of 293 kidney cells using the techniques. Force was applied to the cells, by using a magnetic manipulator, onto the paramagnetic spheres attached to the cell via cellular integrin receptors. The deformation of the cytoskeleton was monitored by following the motion of nearby attached fluorescent polystyrene spheres. We showed that planar stress produces strain in all three dimensions, demonstrating that the 3D motion of the cell is required to fully model cellular mechanical responses.     

Mechanistic insight into the activity of tyrosinase from variable-temperature studies in an aqueous/organic solvent

The activity of mushroom tyrosinase towards a representative series of phenolic and diphenolic substrates structurally related to tyrosine has been investigated in a mixed solvent of 34.4% methanol-glycerol (7:1, v/v) and 65.6% (v/v) aqueous 50 mM Hepes buffer at pH 6.8 at various temperatures. The kinetic activation parameters controlling the enzymatic reactions and the thermodynamic parameters associated with the process of substrate binding to the enzyme active species have been deduced from the temperature variation of the kcat and KM parameters. The activation free energy is dominated by the enthalpic term, the value of which lies in the relatively narrow range of 61+/-9 kJ mol(-1) irrespective of substrate or reaction type (monophenolase or diphenolase). The activation entropies are small and generally negative and contribute no more than 10% to the activation free energy. The substrate binding parameters are characterized by large and negative enthalpy and entropy contributions, which are typically dictated by polar protein-substrate interactions. The substrate 4-hydroxyphenylpropionic acid exhibits a strikingly anomalous temperature dependence of the enzymatic oxidation rate, with deltaH(double dagger) approximately = 150 kJ mol(-1) and deltaS(double dagger) approximately = 280 J K(-1) mol(-1), due to the fact that it can competitively bind to the enzyme through the phenol group, like the other substrates, or the carboxylate group, like carboxylic acid inhibitors. A kinetic model that takes into account the dual substrate/inhibitor nature of this compound enables rationalization of this anomalous behavior.