Dynamics of Parkinsonian tremor during deep brain stimulation

The mechanism by which chronic, high frequency, electrical deep brain stimulation (HF-DBS) suppresses tremor in Parkinson's disease is unknown. Rest tremor in subjects with Parkinson's disease receiving HF-DBS was recorded continuously throughout switching the deep brain stimulator on (at an effective frequency) and off. These data suggest that the stimulation induces a qualitative change in the dynamics, called a Hopf bifurcation, so that the stable oscillations are destabilized. We hypothesize that the periodic stimulation modifies a parameter affecting the oscillation in a time dependent way and thereby induces a Hopf bifurcation. We explore this hypothesis using a schematic network model of an oscillator interacting with periodic stimulation. The mechanism of time-dependent change of a control parameter in the model captures two aspects of the dynamics observed in the data: (1) a gradual increase in tremor amplitude when the stimulation is switched off and a gradual decrease in tremor amplitude when the stimulation is switched on and (2) a time delay in the onset and offset of the oscillations. This mechanism is consistent with these rest tremor transition data and with the idea that HF-DBS acts via the gradual change of a network property. (c) 2001 American Institute of Physics.     

Effects of temperature and pH on the helicity of a peptide adsorbed to colloidal silica

The conformation of a cationic -helical peptide (DDDDAAAARRRRR) adsorbed to anionic colloidal silica has been investigated by circular dichroism (CD) spectroscopy as a function of temperature and pH in order to examine how the structure of an adsorbed molecule responds to two simultaneous perturbations. Increased temperature destabilizes the helicity of the peptide in solution, while pH changes alter the substrate surface charge and the corresponding strength of the interaction with the peptide. Near neutral pH, the helicity of the adsorbed peptide, which is determined from the intensity of the CD signal at 222 nm, decreases with increasing temperature, similarly to the temperature-dependent behavior observed for the peptide in aqueous solution. By contrast, at basic pH and a strongly negative surface charge, the helicity of the adsorbed peptide increases with temperature. In order to elucidate the origin of the reversal of the temperature dependence of helicity, a statistical model for the conformation of the adsorbed peptide has been formulated based on the Lifson–Roig model for the helix–coil transition of the peptide in solution. The model provides insight into the trends in fractional helicity and reveals that the temperature dependence of the helicity of the adsorbed peptide results from a competition between the intramolecular interactions that promote helicity and the intermolecular interactions with the surface. The statistical model also enables estimation of the free energy contributions from specific aspects of the adsorption process. Through identification of a connection between the conformation of adsorbed peptide and the interactions of the peptide with the surface, this work suggests a route for the control of adsorbate conformation through peptide and surface engineering.     

Contribution of EBSD to the Understanding of Massive γ Transformation in TiAl

The massive transformation which occurs after adequate thermal treatment in TiAl alloys with 48 at % Al has been investigated by EBSD analysis. A particular crystallographic relation between the _m nucleus and the adjacent ₂ grain has been demonstrated. The relations between adjacent _m domains have also been characterized. These results confirm previous assumptions about the mechanism of the massive transformation.     

Coherent Hall effect in a semiconductor superlattice

The coherent Hall effect denotes the transient Hall response of impulsively excited coherent charge-carrier wave packets in a solid. We report the first experimental study of this phenomenon (i) using a semiconductor superlattice in crossed electric and magnetic fields as a model for three-dimensional materials and (ii) employing a contactless optoelectronic technique to probe the transient currents. Two field regimes with distinctly different oscillatory wave packet dynamics are found, separated from each other by a transition region where all oscillations are suppressed.     

A NMR and theoretical study of the aggregates between alkyllithium and chiral lithium amides: control of the topology through a single asymmetric center

The complexes between methyllithium and chiral 3-aminopyrrolidine (3-AP) lithium amides bearing a second asymmetric center on their lateral amino group were studied using multinuclear ((1)H, (6)Li, (13)C, (15)N) low-temperature NMR spectroscopies in tetrahydrofuran-d(8). The results indicate that lithium chelation forces the pyrrolidine ring of the 3-AP to adopt a norbornyl-like conformation and that robust 1:1 noncovalent complexes between methyllithium and 3-AP lithium amides form in the medium. A set of (1)H-(1)H and (1)H-(6)Li NMR cross-coupling correlations shows that the binding of methyllithium can take place along the "exo" or the "endo" face of this puckered structure, depending on the relative configuration of the lateral chiral group. This aggregation step renders the nitrogen of the 3-amino group chiral, the "exo" and "endo" topologies corresponding to the (S) and (R) configurations, respectively, of this atom. Density functional theory calculations show that the "exo" and "endo" arrangements are, for both diastereomers, almost isoenergetic even when solvent is taken into account. This result suggests that the formation of the mixed aggregates is under strict kinetic control. A relationship between the topology of these complexes and the sense of induction in the enantioselective alkylation of aromatic aldehydes by alkyllithiums is proposed.     

Alkylating capacity and reaction products of antimalarial trioxanes after activation by a heme model

The reactivity of 1,2,4-trioxane molecules 2-5, structurally related to the antimalarial drug artemisinin, with a heme model, manganese(II) tetraphenylporphyrin, is reported. With the pharmacologically active drugs 2-4, covalent adducts were obtained by addition of a drug-derived radical onto the porphyrin macrocycle, whereas no reaction was obtained with the nonactive compound 5. This confirms that alkylation is probably one of the key factors of the pharmacological activity of endoperoxide-based antimalarial drugs.     

Investigation of the Interactions of Polyvinylpyrrolidone with Mixtures of Anionic and Nonionic Surfactants or Anionic and Zwitterionic Surfactants by Pulsed Field Gradient NMR

The interaction of polyvinylpyrrolidone (PVP) with an anionic surfactant (sodium dodecyl sulfate, SDS), a nonionic surfactant (pentaethylene glycol monodecyl ether, C(10)E(5)), and a zwitterionic surfactant (lauryl amido propyl betaine, LAPB) has been investigated by means of pulsed gradient spin-echo NMR (FT-PGSE NMR), allowing self-diffusion coefficients to be determined. The results confirm the strong interaction prevailing in the PVP/SDS system, whereas no association has been observed in the PVP/C(10)E(5) and PVP/LAPB systems. Mixing PVP with two surfactants, namely SDS and C(10)E(5) or SDS and LAPB, results in the formation of ternary aggregates between the polymer and the mixed micelles. Copyright 2001 Academic Press.