A matrix isolation study of the C(s) symmetric OCNO(X 2A') radical

Here we report the first experimental detection of the C(s) symmetric nitroformyl radical, OCNO(X 2A') in a nitrogen-carbon dioxide matrix at 10 K using a Fourier transform infrared spectrometer (FTIR). The nu1 vibrational frequency was observed at 2113 cm(-1). This assignment was confirmed by follow-up experiments using isotopically labeled reactant molecules (15N, 18O, 13C). To synthesize this radical, we irradiated solid nitrogen-carbon dioxide ice mixtures with energetic electrons at 10 K. Suprathermal nitrogen atoms in their electronic ground and/or first electronically excited state were generated via the radiation induced degradation of molecular nitrogen; these atoms could then react with carbon dioxide to eventually yield the nitroformyl radical. We also investigated the kinetics of the formation of the nitroformyl radical and support the arguments with computations on the doublet and quartet OCNO potential energy surfaces (PESs).     

Integration of spectral and temporal cues separated in time and frequency

Subjects discriminated a "standard" pair of tone bursts (T1, T2) from a "comparison" pair (T1 + delta t, T2 + delta f), containing increments in the duration delta t of the first burst and/or the frequency delta f of the second burst. The threshold (d' = 2.0) for delta t was measured as a function of delta f, and the threshold for delta f as a function of delta t. The integration of increments in duration and frequency was studied as a function of the spectral and temporal separation between T1 and T2. A trade-off between the values of delta t and delta f required for d' = 2.0 performance was observed. This integration takes place when delta t, delta f occur simultaneously in the same spectral region, and when they occur separated by up to 120 ms, or by up to a full octave. The efficiency of integration was similar for all conditions of temporal and spectral separation studied, because the discriminability of delta t and of delta f is also nearly uniform across experimental conditions. The results from all experimental conditions are adequately described by a vector summation model derived from TSD. In a subsidiary experiment, subjects categorized pure tones varying in duration and frequency as "high" or "low" in pitch and "long" or "short" in duration. It was found that combined variations in duration and frequency result in essentially independent perceptual processes, although pitch has a small effect upon the perceived duration. It is concluded that spectral-temporal integration is a general ability operating in a variety of stimulus conditions.(ABSTRACT TRUNCATED AT 250 WORDS)     

The thermal degradation of copolymers of vinyl acetate with methyl methacrylate and other monomers

The thermal degradation of copolymers of vinyl acetate with methyl methacrylate, styrene and ethylene has been investigated using thermal volatilization analysis and thermogravimetry, together with analysis of volatile and involatile degradation products. All three copolymer systems show some of the features characteristic of the homopolymers of the monomers concerned. There is evidence, however, for an intramolecular lactonization process in VA—MMA copolymers, involving reaction of adjacent VA and MMA units with elimination of methyl acetate. This reaction occurs less readily than the analogous process in vinyl chloride—MMA copolymers. Mechanisms of the various degradation reactions are discussed.     

Incorporation of β-Alanine in Cu(II) ATCUN Peptide Complexes Increases ROS Levels,DNA Cleavage and Antiproliferative Activity**

Redox-active Cu(II) complexes are able to form reactive oxygen species (ROS) in the presence of oxygen and reducing agents. Recently, Faller et al. reported that ROS generation by Cu(II) ATCUN complexes is not as high as assumed for decades. High complex stability results in silencing of the Cu(II)/Cu(I) redox cycle and therefore leads to low ROS generation. In this work, we demonstrate that an exchange of the α-amino acid Gly with the β-amino acid β-Ala at position 2 (Gly2→β-Ala2) of the ATCUN motif reinstates ROS production (^•OH and H₂O₂). Potentiometry, cyclic voltammetry, EPR spectroscopy and DFT simulations were utilized to explain the increased ROS generation of these β-Ala2-containing ATCUN complexes. We also observed enhanced oxidative cleavage activity towards plasmid DNA for β-Ala2 compared to the Gly2 complexes. Modifications with positively charged Lys residues increased the DNA affinity through electrostatic interactions as determined by UV/VIS, fluorescence, and CD spectroscopy, and consequently led to a further increase in nuclease activity. A similar trend was observed regarding the cytotoxic activity of the complexes against several human cancer cell lines where β-Ala2 peptide complexes had lower IC₅₀ values compared to Gly2. The higher cytotoxicity could be attributed to an increased cellular uptake as determined by ICP-MS measurements.     

UV-Induced 1,3,4-Oxadiazole Formation from 5-Substituted Tetrazoles and Carboxylic Acids in Flow

A range of 1,3,4-oxadiazoles have been synthesized using a UV-B activated flow approach starting from carboxylic acids and 5-substituted tetrazoles. The application of UV light represents an attractive alternative to the traditional thermolytic approach and has demonstrated comparable efficiency and versatility, with a diverse substrate scope, including the incorporation of highly substituted amino acids.     

Dependence of the scattering length for hydrogen atoms on effective mass

The possibility that the non-adiabatic correction to the scattering length of a pair of hydrogen atoms interacting via the ground state molecular potential, X¹Σ_g ⁺, of H₂ could be made by replacing the mass of each nucleus by a different effective mass is explored. The Born-Oppenheimer potential with adiabatic, relativistic and radiative corrections is used in calculations of the scattering lengths and the mass-dependent shifts of the rotationless vibrational levels with fixed and varying effective masses. The shifts are compared with established values and it is demonstrated that the semi-classical formula for the scattering length accounts well for the effect of changing the mass. A perturbing potential that is equivalent to a change in mass is derived and it is compared to a published local non-adiabatic potential.     

A Petrov-Galerkin method and boundary approximations for hyperbolic initial boundary-value problems

The Petrov-Galerkin method is used to construct a semidiscrete approximation for hyperbolic systems of equations in one space dimension. Stability is analyzed for the Cauchy problem and for an initial and boundary-value problem with positive and negative characeristic speeds of unequal magnitude. Numerical experiments are conducted on a linear problem to support the stability analysis and to compare the accuracies of various boundary approximations. Experiments on a nonlinear problem check the viability of the best boundary method.     

Ma?analytische Bestimmung des Quecksilbers

Ohne Zusammenfassung     

High-frequency nanostructured magnetic materials for integrated inductors

Electroplating is compatible with the deposition of relatively thick layers i.e. several μm to 10s- of μm. However eddy current losses mean that thick layers will have an inferior frequency response. We have used a low content phosphorous bath together with pulse reverse plating to generate Co-rich and Co-deficient multi-nanolayers of CoP having improved saturation magnetisation and a better frequency response. The plating parameters have been optimised in order to produce a material with low loss, and a high permeability of around 700 retained up to 103 MHz for a sample with a thickness of 1.7 μm and a resistivity of 136 μΩ cm.