Syntheses and characterization of two dioxygen-reactive dinuclear macrocyclic schiff-base copper(I) complexes

The dinuclear copper(I) complex [Cu(2)L(1)(CH(3)CN)(2)](ClO(4))(2) (1, L(1) = 3,6,9,17,20,23-hexaazatricyclo[23.3.1.1]triaconta-1(29),2,9,11(30),12(13),14,16,23,25,27-decaene) has been structurally characterized. As previously described, intramolecular ligand hydroxylation (at the aromatic ring) was observed when 1 was reacted with dioxygen. A stopped-flow analysis of the reaction of 1 with dioxygen under different conditions did not allow a "dioxygen intermediate" to be spectroscopically detected. Detailed NMR and electrochemical data on 1 are also presented and evaluated for the first time. No copper(II) complexes of L(1) could be characterized due to hydrolysis of the compounds. In contrast, complex 2-differing from 1 only in an increase in the size of the chelate rings-did not undergo intramolecular hydroxylation when it was oxidized. The crystal structure of 2 is also described.     

Hyperpolarization of Amino Acids in Water Utilizing Parahydrogen on a Rhodium Nanocatalyst

NMR offers many possibilities in chemical analysis, structural investigations, and medical diagnostics. Although it is broadly used, one of NMR spectroscopies main drawbacks is low sensitivity. Hyperpolarization techniques enhance NMR signals by more than four orders of magnitude allowing the design of new contrast agents. Parahydrogen induced polarization that utilizes the para-hydrogen's singlet state to create enhanced signals is of particular interest since it allows to produce molecular imaging agents within seconds. Herein, we present a strategy for signal enhancement of the carbonyl ¹³C in amino acids by using parahydrogen, as demonstrated for glycine and alanine. Importantly, the hyperpolarization step is carried out in water and chemically unmodified canonical amino acids are obtained. Our approach thus offers a high degree of biocompatibility, which is crucial for further application. The rapid sample hyperpolarization (within seconds) may enable the continuous production of biologically useful probes, such as metabolic contrast agents or probes for structural biology.     

Uniqueness of reconstruction of multiphase morphologies from two-point correlation functions

The restoration of the spatial structure of heterogeneous media, such as composites, porous materials, microemulsions, ceramics, or polymer blends from two-point correlation functions, is a problem of relevance to several areas of science. In this contribution we revisit the question of the uniqueness of the restoration problem. We present numerical evidence that periodic, piecewise uniform structures with smooth boundaries are completely specified by their two-point correlation functions, up to a translation and, in some cases, inversion. We discuss the physical relevance of the results.     

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Analysis of the cellular Aspergillus fumigatus proteome that reacts with sera from rabbits developing an acquired immunity after experimental aspergillosis

Invasive aspergillosis caused by the mould Aspergillus fumigatus is a life‐threatening lung or systemic infection in the immunocompromised host. In this study, a protective immune response against the disease was achieved in two infected rabbits, and the cellular fungal antigenic proteome that mediated such a response was investigated against the background of vaccine development efforts. Altogether, 59 different Aspergillus proteins were found becoming reactive in the course of the developing immunity, many of which are described in this context for the first time. These included proteins related to oxidative stress management, glycolysis and other metabolic pathways. As oxidative stress is suspected to be one of the major defense mechanisms, the results may indicate at least in part a continuous response of the pathogen to evade the host's immune system. In addition, proteins with suspected cell surface association or crucial function for fungal cell development were identified. As these antigens are newly recognized during the process of the developing immunoprotection, they may not only represent valuable infection markers but also importantly broaden the list of possible vaccine candidates.     

Calculation of probability density functions for nonlinear vibration systems

Technical systems are subjected to a variety of excitations that cannot generally be described in deterministic ways. Random excitations such as road roughness, wind gusts or loads on marine structures are commonly described by stochastic differential equations (SDEs). Given a set of SDEs, the main task is in finding probability density functions (PDFs), which yield statistical information about the system states. Monte-Carlo simulations represent a general way of generating PDFs, however, reliable integration methods can be time-consuming for complex systems. An alternative way of finding PDFs lies in the analysis of the Fokker-Planck equation, a partial differential equation of the PDF. Linear problems under Gaussian excitation can be solved analytically, which is the case only for a small class of nonlinear problems. As a result, there are a number of methods of approximating PDFs for general problems. Most of these are restricted to comparably low dimensions, such as d=4 ("curse of dimensionality"), limiting the relevance to technical applications. This paper presents solutions to problems of dimensions up to d=10, applying a Galerkin-method that expands approximate solutions into orthogonal polynomials. Problems include polynomial nonlinearities in damping and restoring terms, such as classical Duffing-elements, as well as other types of nonlinearities, demonstrated on a typical problem in vehicle dynamics. All results are compared with results from Monte-Carlo simulations or exact solutions, where available. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

The adsorption and condensed film formation of cetyltrimethylammonium bromide at the mercury/electrolyte interface

The adsorption of cetyltrimethyammonium bromide (CTAB) on a hanging mercury electrode is studied in various electrolyte systems and temperatures. A condensed film is formed at negative potentials and at room temperature only in the presence of KBr. The decrease of the temperature favors the formation of the condensed film. Hysterisis phenomena are observed during the potential scans at both directions. Capacity time curves at the potentials where the film is formed show a nucleation and growth mechanism, with induction time depending on potential, which has been investigated using Avrami formulation and has been explained as a progressive one-dimensional nucleation with constant growth rate. The nucleation rate increases while moving toward more negative potentials. A linear decrease of the capacitance with time was observed in some cases independent of the measuring potential in a relative large potential range. The different types of micelles can affect the adsorption of CTAB on mercury. An unusual capacitance transient observed at a very narrow negative potential range is attributed to the formation of hemicylinders. The condensed film in the presence of the other electrolytes is observed only at high concentrations (1 M) and very low temperatures (5 degrees C).     

Nonlinear Longitudinal Vibrations of Transversally Polarized Piezoceramics: Experiments and Modeling

Nonlinear behavior of piezoceramics at strong electric fields is a well-known phenomenon and is described by various hysteresis curves. On the other hand, nonlinear vibration behavior of piezoceramics at weak electric fields has recently been attracting considerable attention. Ultrasonic motors (USM) utilize the piezoceramics at relatively weak electric fields near the resonance. The consistent efforts to improve the performance of these motors has led to a detailed investigation of their nonlinear behavior. Typical nonlinear dynamic effects can be observed, even if only the stator is experimentally investigated. At weak electric fields, the vibration behavior of piezoceramics is usually described by constitutive relations linearized around an operating point. However, in experiments at weak electric fields with longitudinal vibrations of piezoceramic rods, a typical nonlinear vibration behavior similar to that of the USM-stator is observed at near-resonance frequency excitations. The observed behavior is that of a softening Duffing-oscillator, including jump phenomena and multiple stable amplitude responses at the same excitation frequency and voltage. Other observed phenomena are the decrease of normalized amplitude responses with increasing excitation voltage and the presence of superharmonics in spectra. In this paper, we have attempted to model the nonlinear behavior using higher order (quadratic and cubic) conservative and dissipative terms in the constitutive equations. Hamilton's principle and the Ritz method is used to obtain the equation of motion that is solved using perturbation techniques. Using this solution, nonlinear parameters can be fitted from the experimental data. As an alternative approach, the partial differential equation is directly solved using perturbation techniques. The results of these two different approaches are compared.     

Microfluidic waves

The propagation of pressure waves in fluidic channels with elastic covers is discussed in view of applications to flow control in microfluidic devices. A theory is presented which describes pressure waves in the fluid that are coupled to bending waves in the elastic cover. At low frequencies, the lateral bending of the cover dominates over longitudinal bending, leading to propagating, non-dispersive longitudinal pressure waves in the channel. The theory addresses effects due to both the finite viscosity and compressibility of the fluid. The coupled waves propagate without dispersion, as long as the wave length is larger than the channel width. It is shown that in channels of typical microfluidic dimensions, wave velocities in the range of a few 10 m s(-1) result if the channels are covered by films of a compliant material such as PDMS. The application of this principle to design microfluidic band pass filters based on standing waves is discussed. Characteristic frequencies in the range of a few kHz are readily achieved with quality factors above 30.     

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