High-fidelity Recognition of Organotrifluoroborate Anions (R−BF3−) as Designer Guest Molecules

The recognition of boron compounds is well developed as boronic acids but untapped as organotrifluoroborate anions (R−BF₃⁻). We are exploring the development of these and other designer anions as anion-recognition motifs by considering them as substituted versions of the parent inorganic ion. To this end, we demonstrate strong and reliable binding of organic trifluoroborates, R−BF₃⁻, by cyanostar macrocycles that are size-complementary to the inorganic BF₄⁻ progenitors. We find that recognition is modulated by the substituent's sterics and that the affinities are retained using the common K⁺ salts of R−BF₃⁻ anions.     

Bioanalysis of acetylcarnitine in cerebrospinal fluid by HILIC–mass spectrometry

Acetyl‐l ‐carnitine (ALCAR) is a potential biomarker for the modulation of brain neurotransmitter activity, but is also present in cerebrospinal fluid (CSF). Recent studies have utilized hydrophilic interaction liquid chromatography–tandem mass spectrometry (HILIC‐MS/MS) based assays to detect and quantify ALCAR within biofluids such as urine, plasma and serum, using various sample pretreatment procedures. In order to address the need to quantify ALCAR in CSF on a high‐throughput scale, a new and simple HILIC‐MS/MS assay has been successfully developed and validated. For rapid analysis, CSF sample pretreatment was performed via ‘dilute and shoot’ directly onto an advanced HILIC column prior to MS/MS detection. This newly developed HILIC‐MS/MS assay shows good recoveries of ALCAR without the need for chemical derivatization and multistep sample extraction procedures. The employment of this assay is suitable for the high‐throughput bioanalysis and quantification of ALCAR within the CSF of various animal models and human clinical studies. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis and structural characterization of (η5-Dp)Ru(PPh3)2H (Dp = C8H9−, 1,2-dihydropentalenyl)

Transition Metal Chemistry - (η5-Dp)Ru(PPh3)2H (Dp?=?C8H9?, 1,2-dihydropentalenyl) was synthesized in 90% yield by reaction of (η5-Dp)Ru(PPh3)2Cl with sodium formate....     

The Hausdorff dimension of graphs of Weierstrass functions

The Weierstrass nowhere differentiable function, and functions constructed from similar infinite series, have been studied often as examples of functions whose graph is a fractal. Though there is a simple formula for the Hausdorff dimension of the graph which is widely accepted, it has not been rigorously proved to hold. We prove that if arbitrary phases are included in each term of the summation for the Weierstrass function, the Hausdorff dimension of the graph of the function has the conjectured value for almost every sequence of phases. The argument extends to a much wider class of Weierstrass-like functions.

     

Flatness in analytic mappings I. On an announcement of Hironaka

We present a stratification by “normal flatness” associated to an analytic mapping, analogous to Hironaka's classical result for analytic spaces. Our construction is based on a generic normal flatness theorem for mappings, proved using techniques concerning the variation of modules of meromorphically parametrized formal power series [1]. The existence of such a stratification was announced by Hironaka [13], but the other claims made in [13] are false. Counterexamples are also presented here.     

Enantiodiscrimination of racemic electrophiles by diketopiperazine enolates: asymmetric synthesis of methyl 2-amino-3-aryl-butanoates and 3-methyl-aspartates

Enolates of (S)-N,N′-bis-(p-methoxybenzyl)-3-iso-propylpiperazine-2,5-dione exhibit high levels of enantiodiscrimination in alkylations with (RS)-1-aryl-1-bromoethanes and (RS)-2-bromoesters, affording substituted diketopiperazines containing two new stereogenic centres in high de. Deprotection and hydrolysis of the resultant substituted diketopiperazines provides a route to the asymmetric synthesis of homochiral methyl 2-amino-3-aryl-butanoates and 3-methyl-aspartates in high de and ee.     

Splittings of finitely generated groups over two-ended subgroups

We describe a means of constructing splittings of a one-ended finitely generated group over two-ended subgroups, starting with a finite collection of codimension-one two-ended subgroups. In the case where all the two-ended subgroups have two-ended commensurators, we obtain an annulus theorem, and a form of the JSJ splitting of Rips and Sela. The construction uses ideas from the work of Dunwoody, Sageev and Swenson. We use a particular kind of order structure which combines cyclic orders and treelike structures. In the special case of hyperbolic groups, this provides a link between combinarorial constructions, and constructions arising from the topological structure of the boundary. In this context, we recover the annulus theorem of Scott and Swarup. We also show that a one-ended finitely generated group which contains an infinite-order element, and such that every infinite cyclic subgroup is (virtually) codimension-one is a virtual surface group.