Pentakis-thiacalix[4]Arenes with Nitrile Fragments: Receptor Properties toward Cations of Some s-and d-metals and Self-assembly of Nanoscale Aggregates

Pentakis-thiacalix[4]arenes containing thiacalix[4]arene fragments in cone, partial cone and 1,3-alternate conformations as their central core have been obtained. Their interaction with cations of s- and d-metals gives supramolecular assemblies whose composition depends on the conformation of pentakis-thiacalix[4]arenes and the nature of the ‘guests’.     

A Deployable In Vivo EPR Tooth Dosimeter for Triage After a Radiation Event Involving Large Populations

In order to meet the potential need for emergency large-scale retrospective radiation biodosimetry following an accident or attack, we have developed instrumentation and methodology for in vivo electron paramagnetic resonance spectroscopy to quantify concentrations of radiation-induced radicals within intact teeth. This technique has several very desirable characteristics for triage, including independence from confounding biologic factors, a non-invasive measurement procedure, the capability to make measurements at any time after the event, suitability for use by non-expert operators at the site of an event, and the ability to provide immediate estimates of individual doses. Throughout development there has been a particular focus on the need for a deployable system, including instrumental requirements for transport and field use, the need for high throughput, and use by minimally trained operators.Numerous measurements have been performed using this system in clinical and other non-laboratory settings, including in vivo measurements with unexposed populations as well as patients undergoing radiation therapies. The collection and analyses of sets of three serially-acquired spectra with independent placements of the resonator, in a data collection process lasting approximately five minutes, provides dose estimates with standard errors of prediction of approximately 1 Gy. As an example, measurements were performed on incisor teeth of subjects who had either received no irradiation or 2 Gy total body irradiation for prior bone marrow transplantation; this exercise provided a direct and challenging test of our capability to identify subjects who would be in need of acute medical care.     

Acoustic detection of North Atlantic right whale contact calls using spectrogram-based statistics

This paper considers the problem of detection of contact calls produced by the critically endangered North Atlantic right whale, Eubalaena glacialis. To reduce computational time, the class of acceptable detectors is constrained by the detectors implemented as a bank of two-dimensional linear FIR filters and using the data spectrogram as the input. The closed form representations for the detectors are derived and the detection performance is compared with that of the generalized likelihood ratio test (GLRT) detector. The test results demonstrate that in the presence of impulsive noise, the spectrogram-based detector using the French hat wavelet as the filter kernel outperforms the GLRT detector and decreases computational time by a factor of 6.     

Magnetic properties of rare-earth β-enaminoketone metallomesogens

Reaction of β-enaminoketones with lanthanide salts leads to mesomorphic complexes displaying an S_A mesophase. The mesophase was characterized using X-ray scattering, EPR and magnetic susceptibility. A very high magnetic anisotropy was deduced for a complex containing dysprosium.     

Normal and mixed partial second-order subdifferentials in variational analysis and optimization

A partial second-order subdifferential is defined here for extended real valued functions of two variables corresponding to its variables through coderivatives of first-order partial subdifferential mappings. In addition, some rules are presented to calculate these second-order structures along with defining some conditions to insure the equality \(\partial ^2_{yx}\) and \(\partial ^2_{xy}\). Moreover, as an application, some conditions are stated which show the relation between local minimum of a function and positiveness of principal minors of its hessian matrix.     

Comparative ONIOM modeling of 1,3-butadiene polymerization using Nd(III) and Gd(III) Ziegler–Natta catalyst systems

On the base of structural and thermodynamic data using modern methods of quantum chemistry, a comparative theoretical study of the elementary acts of initiation and growth of a polymer chain during the polymerization of 1,3-butadiene was carried out. Ziegler–Natta catalysts based on Nd(III) and Gd(III) were used as polymerization initiators. It was shown that the higher stereospecificity of the action of gadolinium catalytic complexes in comparison with neodymium complexes is due to the increased stability of the anti-form of the π-allylic terminal structure of the growing polymer chain, and the reduced activity is due to the higher activation energy of the processes of initiation and chain growth.     

A loop resonator for slice-selective in vivo EPR imaging in rats

A loop resonator was developed for 300 MHz continuous-wave electron paramagnetic resonance (CW-EPR) spectroscopy and imaging in live rats. A single-turn loop (55 mm in diameter) was used to provide sufficient space for the rat body. Efficiency for generating a radiofrequency magnetic field of 38 microT/W(1/2) was achieved at the center of the loop. For the resonator itself, an unloaded quality factor of 430 was obtained. When a 350 g rat was placed in the resonator at the level of the lower abdomen, the quality factor decreased to 18. The sensitive volume in the loop was visualized with a bottle filled with an aqueous solution of the nitroxide spin probe 3-carbamoyl-2,2,5,5-tetramethyl-3-pyrrolin-1-yloxy (3-CP). The resonator was shown to enable EPR imaging in live rats. Imaging was performed for 3-CP that had been infused intravenously into the rat and its distribution was visualized within the lower abdomen.