Thermal Cyclization of 2-Acyl-1-azido-3-phenalenones to Phenaleno[1,2-c]isoxazol-7-ones

1-Azido-3-phenalenones 5 with acyl substituents in position 2, obtained by acylation and azidation of 1-hydroxy-3-phenalenones 1 , cyclized by thermolysis to give phenaleno[1,2-c]isoxazol-7-ones 9 . The thermolysis conditions were studied by differential scanning calorimetry.     

Some results for non-linear elliptic problems with mixed boundary conditions

We prove existence and uniqueness results for non-linear elliptic equations with lower order terms, L¹ data, and mixed boundary conditions that include as particular cases the Dirichlet and the Neumann problems. Mathematics Subject Classification (2000) 35J25, 35D05, 35J70, 35J60     

Semiclassical structure of chaotic resonance eigenfunctions

We study the resonance (or Gamow) eigenstates of open chaotic systems in the semiclassical limit, distinguishing between left and right eigenstates of the nonunitary quantum propagator and also between short-lived and long-lived states. The long-lived left (right) eigenstates are shown to concentrate as variant Planck's over 2pi-->0 on the forward (backward) trapped set of the classical dynamics. The limit of a sequence of eigenstates [psi(variant Planck's over)] 2pi-->0 is found to exhibit a remarkably rich structure in phase space that depends on the corresponding limiting decay rate. These results are illustrated for the open baker's map, for which the probability density in position space is observed to have self-similarity properties.     

Stable isotope-free quantitative shotgun proteomics combined with sample pattern recognition for rapid diagnostics

Mass spectrometry (MS) has become a powerful tool for the quantitative analysis of complex protein samples. A high-throughput strategy for the comparative analysis of multiple protein samples with high complexity becomes more and more important. Two strategies, spectral count and peak intensity, for label-free MS analysis of prefractionated complex mixtures have been described recently to be useful for quantitation. Here we compare both strategies for rapid and quantitative 1-D shotgun LC/MS/MS analyses of highly complex protein mixtures using silica-based monolithic columns. First, we validated linearity and sensitivity of these methods by spiking varying amounts of an internal standard protein in a complex plant protein extract. Secondly, quantitative data of proteins of Medicago truncatula nodules were visualized with independent components analysis using data either obtained from spectral count or peak integration performed with commercial software. Spectral count showed apparent advantages over peak integration because several peptides per protein are automatically averaged, the linear dynamic range of quantitation increases in complex matrices and the number of quantified proteins surpasses the number of proteins using peak integration. Thus, for the need of rapid comparative analysis of highly complex protein samples, spectral count enables sample pattern recognition and identification of biomarkers in nongel based proteomic studies.     

Supramolecular stabilization of hydroxylamine TEMPOH by complexation with an amphiphilic calixarene

In an ethanol/water mixture, the nitroxyl radical TEMPO abstracts a hydrogen atom from a phenolic OH group of the amphiphilic para-hexanoylcalix[4]arene, and the hydroxylamine TEMPOH formed yields a stable inclusion complex with another molecule of the calixarene.     

Analytical platforms for activity-based protein profiling--exploiting the versatility of chemistry for functional proteomics

The field of proteomics aims to develop and apply technologies for the characterization of protein function on a global scale. Toward this end, synthetic chemistry has played a major role by providing new reagents to profile segments of the proteome based on activity rather than abundance. Small molecule probes for activity-based protein profiling have been created for more than a dozen enzyme classes and used to discover several enzyme activities elevated in disease states. These innovations have inspired complementary advancements in analytical chemistry, where new platforms have been introduced to augment the information content achievable in chemical proteomics experiments. Here, we will review these analytical platforms and discuss how they have exploited the versatility of chemical probes to gain unprecedented insights into the function of proteins in biological samples of high complexity.     

Two-dimensional wave patterns of spreading depolarization: Retracting, re-entrant, and stationary waves

We present spatio-temporal characteristics of spreading depolarizations (SD) in two experimental systems: retracting SD wave segments observed with intrinsic optical signals in chicken retina, and spontaneously occurring re-entrant SD waves that repeatedly spread across gyrencephalic feline cortex observed by laser speckle flowmetry. A mathematical framework of reaction-diffusion systems with augmented transmission capabilities is developed to explain the emergence and transitions between these patterns. Our prediction is that the observed patterns are reaction-diffusion patterns controlled and modulated by weak nonlocal coupling such as long-range, time-delayed, and global coupling. The described spatio-temporal characteristics of SD are of important clinical relevance under conditions of migraine and stroke. In stroke, the emergence of re-entrant SD waves is believed to worsen outcome. In migraine, retracting SD wave segments cause neurological symptoms and transitions to stationary SD wave patterns may cause persistent symptoms without evidence from noninvasive imaging of infarction.