Synthesis and reactivity of 4-chloro-3,3,4-trifluoro-methoxycarbonyl cyclobutene (CTMC)

An improved synthesis of CTMC is described. This cyclobutene is thermally stable towards electrocyclic ring opening. Its reactivity is explored and a number of radical adducts are described. A more complicated picture is observed with various nucleophiles. The strong dienophilic character of CTMC is illustrated by numerous examples. CTMC reacts well as a dipolarophile with diphenylnitrone, diphenylnitrilimine and diazoalkanes. The high reactivity of this cyclobutene is due to its inherent polarity and strain.     

A Novel Coenzyme A Analogue in the Anaerobic,Sulfate-Reducing,Marine Bacterium Desulfobacula toluolica Tol2T

Coenzyme A (CoA) thioesters are formed during anabolic and catabolic reactions in every organism. Degradation pathways of growth-supporting substrates in bacteria can be predicted by differential proteogenomic studies. Direct detection of proposed metabolites such as CoA thioesters by high-performance liquid chromatography coupled with high-resolution mass spectrometry can confirm the reaction sequence and demonstrate the activity of these degradation pathways. In the metabolomes of the anaerobic sulfate-reducing bacterium Desulfobacula toluolica Tol2^T grown with different substrates various CoA thioesters, derived from amino acid, fatty acid or alcohol metabolism, have been detected. Additionally, the cell extracts of this bacterium revealed a number of CoA analogues with molecular masses increased by 1 dalton. By comparing the chromatographic and mass spectrometric properties of synthetic reference standards with those of compounds detected in cell extracts of D. toluolica Tol2^T and by performing co-injection experiments, these analogues were identified as inosino-CoAs. These CoA thioesters contain inosine instead of adenosine as the nucleoside. To the best of our knowledge, this finding represents the first detection of naturally occurring inosino-CoA analogues.     

Deducing the Fatigue Crack Growth Rates of Natural Flaws in Silicon Nitride Ceramics: Role of R‐Curves

Fatigue failure is a concern when high‐strength, high‐toughness silicon nitride ceramics are used in mechanical components and the growth of natural flaws will determine the usable upper bound strength. In this study a fracture resistance curve (R‐curve) model is incorporated into an established method for deducing natural flaw growth rates from a combination of strength and fatigue life data for smooth specimens. Experimental data for a commercial silicon nitride, SL200, were examined. When compared with results deduced using a constant fracture toughness model, the new method gives more physically realistic growth rate results. Specifically, by incorporating the R‐curve the deduced fatigue threshold is equal to the reported intrinsic toughness for crack propagation of 2.2 MPa√m, whereas the constant fracture toughness model gives a physically unrealistic threshold value. Furthermore, much better agreement is achieved with the growth rates measured using macroscopic compact‐tension specimens. Overall, it is concluded that the R‐curve effect should not be ignored when deducing the fatigue crack growth rates of natural flaws in high‐toughness silicon nitride ceramics.     

Mathematical Description of Experimentally Determined Charge Distributions of a Unipolar Diffusion Charger

The charge distributions of an improved opposed flow unipolar diffusion charger were measured using a tandem differential mobility analyzer (DMA) set up in a size range of approximately 20–400 nm. The charger is intended to be used in a portable aerosol sizer to measure particle size distributions. The determined charge distributions were represented by lognormal distributions, and a set of equations and coefficients was developed to calculate the charge distributions. These equations can be easily implemented in software for size distribution measurements. The agreement between the mathematically derived and measured charge distributions is very good, with regression coefficients R ² > 0.96. The investigations showed that approximately 55% of 20-nm particles remain uncharged, while up to 25 elementary charges need to be considered for multiple charge correction of 400-nm particles. Comparison with the Fuchs theory delivered satisfying agreement with the measured average charge levels, but charge distributions cannot be described by the Fuchs theory, likely caused by the charger geometry.

Copyright 2012 American Association for Aerosol Research     

High-temperature gradient HPLC for the separation of polyethylene–polypropylene blends

A high-temperature gradient HPLC method has been developed for the analysis of polyethylene–polypropylene blends. For the first time it was possible to separate these polyolefin blends by a chromatographic technique which is operating at 140 °C. Blends of a commercial polypropylene and a medium molar mass linear polyethylene were separated using a mobile phase of ethylene glycol monobutylether (EGMBE) and 1,2,4-trichlorobenzene (TCB) and silica gel as the stationary phase. With the use of n-decanol as sample solvent, a precipitation–redissolution mechanism for polyethylene (PE) was established while polypropylene (PP) is eluted in size exclusion mode.     

A Unified Model for the Mixing of Non‐Newtonian Fluids in the Laminar,Transition, and Turbulent Region

Summary: Non‐Newtonian fluid behavior has significant influence on quantities in chemical engineering like power input, mixing time, heat transfer etc. In the laminar flow region, the concept of effective viscosity by Metzner and Otto is well established. In the transition region between laminar and turbulent flow, the existing concepts use three and even more empirical parameters to determine the specific power input. Here, a unified and general but simple approach is introduced to calculate the power input for shear thinning fluids over the whole flow region using just one empirical parameter. The Metzner‐Otto relation is obtained as a limiting case for the laminar region. The empirical parameter of the new approach is related to the Metzner‐Otto constant. The concept is validated for eight different stirrer systems. Mixing time and maximum shear rate and heat transfer can also be calculated using this approach. The new concept presented should also be applicable for other apparatuses, e.g., static mixers.

Comparison of experimental data and a curve calculated according to the new method (solid line).     

The critical role of water in spider silk and its consequence for protein mechanics

Due to its remarkable mechanical and biological properties, there is considerable interest in understanding, and replicating, spider silk's stress-processing mechanisms and structure-function relationships. Here, we investigate the role of water in the nanoscale mechanics of the different regions in the spider silk fibre, and their relative contributions to stress processing. We propose that the inner core region, rich in spidroin II, retains water due to its inherent disorder, thereby providing a mechanism to dissipate energy as it breaks a sacrificial amide-water bond and gains order under strain, forming a stronger amide-amide bond. The spidroin I-rich outer core is more ordered under ambient conditions and is inherently stiffer and stronger, yet does not on its own provide high toughness. The markedly different interactions of the two proteins with water, and their distribution across the fibre, produce a stiffness differential and provide a balance between stiffness, strength and toughness under ambient conditions. Under wet conditions, this balance is destroyed as the stiff outer core material reverts to the behaviour of the inner core.     

Praxisnahe Bestimmung von Wärmeübergangskoeffizienten an Körpern unterschiedlicher Geometrie

A simple method is presented by which the mean heat transfer coefficient at arbitrary geometries in a steady flow field can be determined. It is based on the measurement of the time dependent temperature and an evaluation that takes into account the conservation of thermal energy. For spheres of various sizes the method is exemplified demonstrating that the results agree well with those from the heat transfer literature.