Separable Groupoid Rings

We show that groupoid rings are separable over their ring of coefficients if and only if the groupoid is finite and the orders of the associated principal groups are invertible in the ring of coefficients. We use this to show that if we are given a finite groupoid, then the associated groupoid ring is semisimple (or hereditary) if and only if the ring of coefficients is semisimple (or hereditary) and the orders of the principal groups are invertible in the ring of coefficients. To this end, we extend parts of the theory of graded rings and modules from the group graded case to the category graded, and, hence, groupoid graded situation. In particular, we show that strongly groupoid graded rings are separable over their principal components if and only if the image of the trace map contains the identity.     

Total synthesis of diaportheone A

Diaportheone A (1), a chromone natural product was previously isolated from the endophytic fungi Diaporthe sp. P 133. Its structure was established by spectroscopic methods, however, its absolute configuration remained undefined. This study dealt on the total synthesis of diaportheone A (1) utilizing the cyclization and in situ thermal syn-elimination of a β-ketosulfoxide. The C-1R absolute configuration of the natural product was established by X-ray crystallography of the synthetic diaportheone A (1) (>99%?ee) and comparison with the optical rotation.     

Mechanism and kinetics of thermal degradation of insulating materials developed from cellulose fiber and fire retardants

The mechanism and kinetics of thermal degradation of materials developed from cellulose fiber and synergetic fire retardant or expandable graphite have been investigated using thermogravimetric analysis. The model-free methods such as Kissinger–Akahira–Sunose (KAS), Friedman, and Flynn–Wall–Ozawa (FWO) were applied to measure apparent activation energy (E_α). The increased E_α indicated a greater thermal stability because of the formation of a thermally stable char, and the decreased E_α after the increasing region related to the catalytic reaction of the fire retardants, which revealed that the pyrolysis of fire retardant-containing cellulosic materials through more complex and multi-step kinetics. The Friedman method can be considered as the best method to evaluate the E_α of fire-retarded cellulose thermal insulation compared with the KAS and FWO methods. A master-plots method such as the Criado method was used to determine the possible degradation mechanisms. The degradation of cellulose thermal insulation without a fire retardant is governed by a D3 diffusion process when the conversion value is below 0.6, but the materials containing synergetic fire retardant and expandable graphite fire retardant may have a complicated reaction mechanism that fits several proposed theoretical models in different conversion ranges. Gases released during the thermal degradation were identified by pyrolysis–gas chromatography/mass spectrometry. Fire retardants could catalyze the dehydration of cellulosic thermal insulating materials at a lower temperature and facilitate the generation of furfural and levoglucosenone, thus promoting the formation of char. These results provide useful information to understand the pyrolysis and fire retardancy mechanism of fire-retarded cellulose thermal insulation.

     

A Neutral η5‐Aminoborole Complex of Germanium(II)

The synthesis of two η⁵‐aminoborole complexes of germanium(II) from the reaction of a germole dianion with aminoboron dichlorides is reported. This reaction constitutes a remarkable example of a germole‐to‐borole transformation. The two aminoborole complexes of germanium(II) were fully characterized by multinuclear NMR spectroscopy, IR spectroscopy, HRMS, and, in one case, by X‐ray crystallography. The results of quantum‐mechanical calculations favor the electronic structure of a half‐sandwich complex of Ge^II over an ionic representation with a germanium dication stabilized by an aromatic aminoborole dianion.     

Isotope exchange and structural rearrangements in reactions between size-selected ionic water clusters, H3O(+)(H2O)(n) and NH4(+)(H2O)(n), and D2O

Hydrogen/deuterium exchange in reactions of H3O(+)(H2O)n and NH4(+)(H2O)n (1 < or = n < or = 30) with D2O has been studied experimentally at center-of-mass collisions energies of < or = 0.2 eV. For a given cluster size, the cross-sections for H3O(+)(H2O)n and NH4(+)(H2O)n are similar, indicating a structural resemblance and energetics of binding. For protonated pure water clusters, H3O(+)(H2O)n, reacting with D2O the main H/D exchange mechanism is found to be proton catalyzed. In addition the H/D scrambling becomes close to statistically randomized for the larger clusters. For NH4(+)(H2O)n clusters reacting with D2O, the main mechanism is a D2O/H2O swap reaction. The lifetimes of H3O(+)(H2O)n clusters have been estimated using RRKM theory and a plateau in lifetime vs. cluster size is found already at n = 10.     

Comparative study of the photochemistry of the azidopyridine 1-oxides

The photochemistry of azidopyridine 1-oxides was studied using an array of glass and matrix isolation techniques. As with room temperature, the photochemistry of 4-azidopyridine 1-oxide is dominated by triplet nitrene chemistry. However, in the case of the 3-azide, matrix photolysis indicates the formation of diazabicyclo[4.1.0]hepta-2,4,6-triene N-oxide and diazacycloheptatetraene N-oxide intermediates as well as triplet nitrene.     

Errata to: “Vector-valued Modulation Spaces and Localization Operators with Operator-valued Symbols”

In our article “Vector-valued Modulation Spaces and Localization Operators with Operator-valued Symbols”, Integr. equ. oper. theory 59 (1) (2007), 99–128, Example 4.4 is false. We present a corrected example.      

Probing chemical shifts of invisible states of proteins with relaxation dispersion NMR spectroscopy: how well can we do?

Carr-Purcell-Meiboom-Gill relaxation dispersion NMR spectroscopy has evolved into a powerful approach for the study of low populated, invisible conformations of biological molecules. One of the powerful features of the experiment is that chemical shift differences between the exchanging conformers can be obtained, providing structural information about invisible excited states. Through the development of new labeling approaches and NMR experiments it is now possible to measure backbone 13C(alpha) and 13CO relaxation dispersion profiles in proteins without complications from 13C-13C couplings. Such measurements are presented here, along with those that probe exchange using 15N and 1HN nuclei. A key experimental design has been the choice of an exchanging system where excited-state chemical shifts were known from independent measurement. Thus it is possible to evaluate quantitatively the accuracy of chemical shift differences obtained in dispersion experiments and to establish that in general very accurate values can be obtained. The experimental work is supplemented by computations that suggest that similarly accurate shifts can be measured in many cases for systems with exchange rates and populations that fall within the range of those that can be quantified by relaxation dispersion. The accuracy of the extracted chemical shifts opens up the possibility of obtaining quantitative structural information of invisible states of the sort that is now available from chemical shifts recorded on ground states of proteins.     

Free‐Standing Membranes to Study the Optical Properties of Anodic TiO2 Nanotube Layers

In the present work we investigate various optical properties (such as light absorption and reflectance) of anodic TiO₂ nanotube layers directly transferred as self‐standing membranes onto quartz substrates. This allows investigation in a transmission geometry which provides significantly more reliable data than measurements on the metallic Ti substrate. Light transmission and reflectance measurements were carried out for layers of thickness varying from 1.8 to 50 μm, and the layers were investigated in their amorphous and crystalline forms. A series of wavelength‐dependent light attenuation coefficients are extrapolated and found to match the photocurrent versus irradiation wavelength behavior. A feature specific to anodic nanotubes is that their intrinsic carbon contamination content causes a proportional sub‐bandgap response. Overall, the extracted data provide a valuable basis and understanding for the design of photo‐electrochemical devices based on TiO₂ nanotubes.