Mode Localization Induced by a Nonlinear Control Loop

We present the analysis of a nonlinear controlsystem that is used to excite and maintain a specified amplitude ofoscillation in the Jet Propulsion Laboratory vibratory gyroscope.This experimental application shows that nonlinear localizationthrough active means can be implemented in a practical system when itis desirable to confine the response to a favorable mode. Theclosed-loop system response predicted by the model shows very closeagreement with the experimental results for a significant range ofcontroller parameters. We also experimentally demonstrate that theactively localized motion is eliminated through bifurcation, similarto what was observed in previous passive localization studies appliedto extended flexible oscillators.     

Polypeptide folding on a conformational‐space network: Dependence of network topology on the structural discretization procedure

Mapping the conformational space of a polypeptide onto a network of conformational states involves a number of subjective choices, mostly in relation to the definition of conformation and its discrete nature in a network framework. Here, we evaluate the robustness of the topology of conformational‐space networks derived from Molecular Dynamics (MD) simulations with respect to the use of different discretization (clustering) methods, variation of their parameters, simulation length and analysis time‐step, and removing high‐frequency motions from the coordinate trajectories. In addition, we investigate the extent to which polypeptide dynamics can be reproduced on the resulting networks when assuming Markovian behavior. The analysis is based on eight 500 ns and eight 400 ns MD simulations in explicit water of two 10‐residue peptides. Three clustering algorithms were used, two of them based on the pair‐wise root‐mean‐square difference between structures and one on dihedral‐angle patterns. A short characteristic path length and a power‐law behavior of the probability distribution of the node degree are obtained irrespective of the clustering method or the value of any of the tested parameters. The average cliquishness is consistently one or two orders of magnitude larger than that of a random realization of a network of corresponding size and connectivity. The cliquishness as function of node degree and the kinetic properties of the networks are found to be most dependent on clustering method and/or parameters. Although Markovian simulations on the networks reproduce cluster populations accurately, their kinetic properties most often differ from those observed in the MD simulations. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010     

Analysis of the temperature dependence of the high-frequency EMR spectra of Mn ions in the lithium-ion battery material LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript>

This paper deals with the analysis of the temperature dependence of high-frequency EMR (HF-EMR) spectra due to Mn³⁺ and Mn⁴⁺ ions in the lithium manganese spinel LiMn₂O₄. A range of powder samples obtained by the sol-gel method with calcinations in several temperature ranges were prepared for this study. Based on the initial characterization carried out by a number of techniques, the physicochemical and structural properties of the samples were earlier determined. Independently, temperature magnetization and HF-EMR measurements were carried out. The EMR spectra vary strongly between samples, indicating possible structural or chemical changes. Quantitative analysis of the temperature dependence of the HF-EMR spectra due to Mn³⁺ and Mn⁴⁺ ions in LiMn₂O₄ is presented in this paper. The spectral analysis concerns the line shape, linewidth, intensity and g-factors. Fittings using the Lorentzian spectral shape and, to a certain extent, the Gaussian spectral shape have been carried out in order to parameterize the temperature dependence of the HF-EMR spectra. This parameterization of the HF-EMR experimental data enables a deeper characterization of the samples. Subsequently, a better insight into the role of the Mn³⁺ and Mn⁴⁺ ions in accounting for the characteristics most suitable for application of LiMn₂O₄ as a cathode material may be gained.     

DMSA and its complexes with radioisotopes: review

Meso-2,3-dimercaptosuccinic acid (DMSA) forms stable complexes with a remarkable wide range of metal ions. This relatively small molecule has attracted increasing attention in the field of radiopharmacy, treatment of heavy metal intoxications and nanoparticles preparation. In this review detailed summary of all physical, chemical and biological properties of DMSA and its complex compounds with ^99mTc, ^186/188Re, ¹⁶⁶Ho, ¹⁷⁷Lu and ⁹⁰Y is provided. The clinical utilisation of DMSA complexes in the nuclear medicine and its use for treatment of heavy metal intoxication is briefly summarised. The aspects of its application in the field of nanoparticles preparation is behind the scope of this review, therefore it is only shortly described.     

On the implicit bond-dependency origins of bridge interactions

The indirect (through-bridge) components of chemical interactions between atomic orbitals (AO) are shown to originate from the indirect dependencies between AO due to the orbital intermediaries in the bond system of the molecule. They are expressed in terms of the bridge-coupling elements of the density matrix via the chain rule transformation of the implicit derivatives between the indirectly bonded AO in the molecular bond system. The elements of the charge-and-bond-order (CBO) matrix are interpreted as the canonical derivatives between the AO-projections onto the bond subspace combining the occupied Molecular Orbitals (MO). The chain-rule manipulations are then used to express the scattering amplitudes via AO intermediaries in terms of the relevant elements of the CBO matrix. The squares of such amplitudes are related to the Wiberg-type indirect bond components, which complement the familiar direct Wiberg bond-order contributions. The interference implications of the probability scatterings via the multiple cascades involving all basis functions are examined. These probability propagations are shown to preserve the stationary conditional probabilities of the underlying molecular communication channel in AO resolution.     

Homomorphisms and boundedness in topological groups

We consider homomorphisms from a normed space into a topological group. Assuming their boundedness in a neighbourhood (in relative topology) of an extremal point of the unit sphere, we derive their linearity (whenever it makes sense), closedness of the graph or continuity.     

Dynamic Ion Speciation during the Hydrolysis of Aryltrifluoroborates**

Organotrifluoroborates serve as coupling partners during transmetalation in the Suzuki–Miyaura reaction but require hydrolysis prior to the coupling reaction. Their anionic nature allows study of their hydrolysis by electrospray ionization mass spectrometry (ESI-MS) through real-time monitoring, complemented by pH analysis. The induction period varied according to the borates employed, and a dynamic series of equilibria for numerous ions was observed during hydrolysis. We found that the induction periods and reaction rates were sensitive to the R group of the borates, the shape of the reaction vessel, and stir rate.