Dynamic Ion Speciation during the Hydrolysis of Aryltrifluoroborates**

Organotrifluoroborates serve as coupling partners during transmetalation in the Suzuki–Miyaura reaction but require hydrolysis prior to the coupling reaction. Their anionic nature allows study of their hydrolysis by electrospray ionization mass spectrometry (ESI-MS) through real-time monitoring, complemented by pH analysis. The induction period varied according to the borates employed, and a dynamic series of equilibria for numerous ions was observed during hydrolysis. We found that the induction periods and reaction rates were sensitive to the R group of the borates, the shape of the reaction vessel, and stir rate.     

Carbon Materials for Lithium Sulfur Batteries—Ten Critical Questions

Lithium–sulfur batteries are among the most promising electrochemical energy storage devices of the near future. Especially the low price and abundant availability of sulfur as the cathode material and the high theoretical capacity in comparison to state‐of‐the art lithium‐ion technologies are attractive features. Despite significant research achievements that have been made over the last years, fundamental (electro‐) chemical questions still remain unanswered. This review addresses ten crucial questions associated with lithium–sulfur batteries and critically evaluates current research with respect to them. The sulfur–carbon composite cathode is a particular focus, but its complex interplay with other hardware components in the cell, such as the electrolyte and the anode, necessitates a critical discussion of other cell components. Modern in situ characterisation methods are ideally suited to illuminate the role of each component. This article does not pretend to summarise all recently published data, but instead is a critical overview over lithium–sulfur batteries based on recent research findings.     

A note on records in a random sequence

In an infinite sequence of independent identically distributed continuous random variables we study the number of strings of two subsequent records interrupted by a given number of non-records. By embedding in a marked Poisson process we prove that these counts are independent and Poisson distributed. Also the distribution of the number of uninterrupted strings of records is considered.     

Positivity preserving finite element approximation

We consider finite element operators defined on ``rough' functions in a bounded polyhedron in . Insisting on preserving positivity in the approximations, we discover an intriguing and basic difference between approximating functions which vanish on the boundary of and approximating general functions which do not. We give impossibility results for approximation of general functions to more than first order accuracy at extreme points of . We also give impossibility results about invariance of positive operators on finite element functions. This is in striking contrast to the well-studied case without positivity.

     

Taylor dispersion monitored by electrospray mass spectrometry: a novel approach for studying diffusion in solution

This work describes a novel approach for monitoring analyte diffusion in solution that is based on electrospray ionization mass spectrometry (ESI-MS). A mass spectrometer at the end of a laminar flow tube is used to measure the Taylor dispersion of an initially sharp boundary between two solutions of different analyte concentration. This boundary is dispersed by the laminar flow profile in the tube. However, this effect is diminished by analyte diffusion that continuously changes the radial position, and hence the flow velocity of individual analyte molecules. The steepness of the resulting dispersion profile therefore increases with increasing diffusion coefficient of the analyte. A theoretical framework is developed to adapt the equations governing the dispersion process to the case of mass spectrometric detection. This novel technique is applied to determine the diffusion coefficients of choline and cytochrome c. The measured diffusion coefficients, (11.9 +/- 1.0) x 10(-10) m(2) s(-1) and (1.35 +/- 0.08) x 10(-10) m(2) s(-1), respectively, are in agreement with the results of control experiments where the Taylor dispersion of these two analytes was monitored optically. Due to the inherent selectivity and sensitivity of ESI-MS, it appears that the approach described in this work could become a valuable alternative to existing methods for studying diffusion processes, especially for experiments on multicomponent systems.     

Separability and the Twisted Frobenius Bimodule

This paper begins with an introduction to -Frobenius structure on a finite-dimensional Hopf subalgebra pair. In Section 2 a study is made of a generalization of Frobenius bimodules and -Frobenius extensions. Also a special type of twisted Frobenius bimodule which gives an endomorphism ring theorem and converse is studied. Section 3 brings together material on separable bimodules, the dual definitions of split and separable extension, and a theorem of Sugano on endomorphism rings of separable bimodules. In Section 4, separable twisted Frobenius bimodules are characterized in terms of data that generalizes a Frobenius homomorphism and a dual base. In the style of duality, two corollaries characterizing split -Frobenius and separable -Frobenius extensions are proven. Sugano"s theorem is extended to -Frobenius extensions and their endomorphism rings. In Section 5, the problem of when separable extensions are Frobenius extensions is discussed. A Hopf algebra example and a matrix example are given of finite rank free separable -Frobenius extensions which are not Frobenius in the ordinary sense.