Repurposing the Pummerer Rearrangement: Determination of Methionine Sulfoxides in Peptides

The reversible oxidation of methionine residues in proteins has emerged as a biologically important post-translational modification. However, detection and quantitation of methionine sulfoxide in proteins is difficult. Our aim is to develop a method for specifically derivatizing methionine sulfoxide residues. We report a Pummerer rearrangement of methionine sulfoxide treated sequentially with trimethylsilyl chloride and then 2-mercaptoimidazole or pyridine-2-thiol to produce a dithioacetal product. This derivative is stable to standard mass spectrometry conditions, and its formation identified oxidized methionine residues. The scope and requirements of dithioacetal formation are reported for methionine sulfoxide and model substrates. The reaction intermediates have been investigated by computational techniques and by ¹³C NMR spectroscopy. These provide evidence for an α-chlorinated intermediate. The derivatization allows for detection and quantitation of methionine sulfoxide in proteins by mass spectrometry and potentially by immunochemical methods.     

Processing and properties of tape-cast alumina/zirconia laminates composites

In the present work, laminar ceramic structures formed by layers of alumina and partially stabilized zirconia were fabricated by water-based tape casting. Rheological, physical and mechanical properties of slurries and laminates were evaluated. The laminates consisted of stacked alumina and zirconia green tapes produced by thermopressing. Pyrolysis was carried out at 450 °C and sintering at 1500 °C. The alumina/zirconia laminates were studied for a better understanding of the formation behavior and crack propagation at the laminate interface. The flexural strength values of laminates depend on the stress state on their surface. The laminates with the highest amount of zirconia layers presented low strength values (6.7 MPa), while the laminates with more alumina layers had a higher strength level (57.7 MPa). This is because these laminates have alumina layers on the surface which are in a state of residual compressive stress.     

How many object colors can we distinguish?

The question of how many different colors humans can perceive has been of interest to philosophers, psychologists and color scientists for centuries. In recent years the question of the number of distinguishable object color stimuli has been addressed by color scientists by defining a distinguishable color as a given stimulus surrounded by the contour of stimuli just noticeably different from the central stimulus. For a particular set of conditions the number of distinguishable object color stimuli assessed in this manner has recently been found to be slightly larger than 2 million. In this article an argument is made that the related rules are arbitrary and unnecessarily limiting. Based on logical arguments and experimental just noticeable difference data it is shown that, for the conditions involved, a more realistic if conservative number of distinguishable object color stimuli is ～40 million. © 2015 Wiley Periodicals, Inc. Col Res Appl, 41, 439–444, 2016     

Argon: Systematic Review on Neuro- and Organoprotective Properties of an “Inert” Gas

Argon belongs to the group of noble gases, which are regarded as chemically inert. Astonishingly some of these gases exert biological properties and during the last decades more and more reports demonstrated neuroprotective and organoprotective effects. Recent studies predominately use in vivo or in vitro models for ischemic pathologies to investigate the effect of argon treatment. Promising data has been published concerning pathologies like cerebral ischemia, traumatic brain injury and hypoxic ischemic encephalopathy. However, models applied and administration of the therapeutic gas vary. Here we provide a systematic review to summarize the available data on argon’s neuro- and organoprotective effects and discuss its possible mechanism of action. We aim to provide a summary to allow further studies with a more homogeneous setting to investigate possible clinical applications of argon.     

The Dysfunctional Leica

Abstract

Winding up the estate of somebody is a sad task, only sustained by the hope of unexpected finds or definitive proof of one's preconceived opinions. There is no difference in this between one's own grandmother and a contemporary like Lucia Moholy. While executing this task I naturally came across various documents that shifted my vague assumptions about this versatile woman in different directions. I saw photographs from her private life that enlightened me about her social relations but, in the end, I was disappointed at not havlng been able to get closer to a person I thought I knew quite well, even if from a certain distance.¹