Weak amenability of CAT(0)-cubical groups

We prove that if G is a discrete group that admits a metrically proper action on a finite-dimensional CAT(0) cube complex X, then G is weakly amenable. We do this by constructing uniformly bounded Hilbert space representations π _z for which the quantities z ^{ℓ (g)} are matrix coefficients. Here ℓ is a length function on G obtained from the combinatorial distance function on the complex X.     

Markovian trees: properties and algorithms

In this paper we introduce a structure called the Markovian tree (MT). We define the MT and explore its alternative representation as a continuous-time Markovian Multitype Branching Process. We then develop two algorithms, the Depth and Order algorithms to determine the probability of eventual extinction of the MT process. We show that both of these algorithms have very natural physically intuitive interpretations and are analogues of the Neuts and U algorithms in Matrix-analytic Methods. Furthermore, we show that a special case of the Depth algorithm sheds new light on the interpretation of the sample paths of the Neuts algorithm.     

The influence of peripheral ligand bulk on nitrogen activation by three‐coordinate molybdenum complexes—A theoretical study using the ONIOM method

Electronic structure methods have been combined with the ONIOM approach to carry out a comprehensive study of the effect of ligand bulk on the activation of dinitrogen with three‐coordinate molybdenum complexes. Calculations were performed with both density functional and CCSD(T) methods. Our results show that not only is there expected destabilization of the intermediate on the pathway due to direct steric interactions of the bulky groups, but also there is significant electronic destabilization as the size of the ligand increases. This latter destabilization is due to the inability of the molecule to accommodate a rotated amide group bound to the molybdenum once the amide reaches a certain size. This destabilization also leads to a clear preference for the triplet intermediate (rather than the singlet intermediate) for bulky substituents which is in agreement with experiment. Overall, the calculated reaction profile for the bulky substituents shows a good correlation with the available experimental data. © 2009 Wiley Periodicals, Inc. J Comput Chem 2009     

ChemInform Abstract: A Matrix Isolation and Computational Study of Molecular Palladium Fluorides: Does PdF6 Exist?

Binary palladium fluorides from PdF to PdF₆ are investigated by matrix‐isolation methods using thermal evaporation and laser ablation to generate Pd atoms for reaction with F₂‐doped Ar and Ne matrices as well as neat F₂ matrices.     

Synthesis and characterisation of trinuclear metal complexes derived from carboxymethyl-substituted sarcophagine macrobicyclic cage amines

The synthesis and single-crystal x-ray structure determination of two new trinuclear metal complexes is detailed. In these we utilise the appended iminodiacetate substituents, in [Co(CH₃)NH(CH₂CO₂H)₂sar]³⁺, to act as a focus for coordination of other metal ions. Thus, we have made complexes of Cu and Ni utilising the basic carbonates of these metals and [Co(CH₃){N(CH₂CO₂H)₂}sar]³⁺ (CoL2) which gave rise to ((CoL2–2H⁺)₂M), M = Cu and Ni. The electrochemical study of the latter was inconclusive and provides the impetus for further study.     

Iridium-catalyzed C-H activation/borylation/oxidation for the preparation of bis-protected phloroglucinol derivatives

The preparation of bis-protected phloroglucinol derivatives from a range of protected resorcinol substrates is presented. Functionalization was achieved via a two-step, one-pot iridium-catalyzed C-H activation/borylation/oxidation protocol. Our system gave high conversions to the arylboronic esters and good yields of the desired phenols following subsequent oxidation. A range of common protecting group categories was studied including alkyl, silyl, ether and ester.     

A comparison of positive and negative ion collision‐induced dissociation for model heptapeptides with one basic residue

The effects of the identity and position of basic residues on peptide dissociation were explored in the positive and negative modes. Low‐energy collision‐induced dissociation (CID) was performed on singly protonated and deprotonated heptapeptides of the type: XAAAAAA, AAAXAAA, AAAAAXA and AAAAAAX, where X is arginine (R), lysine (K) or histidine (H) residues and A is alanine. For [M + H]⁺, the CID spectra are dominated by cleavages adjacent to the basic residues and the majority of the product ions contain the basic residues. The order of a basic residue's influence on fragmentation of [M + H]⁺ is arginine > histidine ≈ lysine, which is also the order of decreasing gas‐phase basicity for these amino acids. These results are consistent with the side chains of basic residues being positive ion charge sites and with the more basic arginine residues having a higher retention (i.e. sequestering) of the positive charge. In contrast, for [M ? H]^? the identity and position of basic residues has almost no effect on backbone fragmentation. This is consistent with basic residues not being negative mode charge sites. For these peptides, more complete series of backbone fragments, which are important in the sequencing of unknowns, can be found in the negative mode. Spectra at both polarities contain C‐terminal y‐ions, but y_n″⁺ has two more hydrogens than the corresponding y_n^?. Another major difference is the production of the N‐terminal backbone series b_n⁺ in the positive mode and c_n^? in the negative mode. Thus, comparison of positive and negative ion spectra with an emphasis on searching for pairs of ions that differ by 2 Da (y_n″⁺ vs y_n^?) and by 15 Da (b_n⁺ vs c_n^?) may be a useful method for determining whether a product ion is generated from the C‐terminal or the N‐terminal end of a peptide. In addition, a characteristic elimination of NH?C?NH from arginine residues is observed for deprotonated peptides. Copyright © 2010 John Wiley & Sons, Ltd.