Gas-phase structures and mass spectra of binary pentafluorides

Most known non-radioactive pentafluorides have been examined by molecular-beam mass spectrometry and by the deflection of molecular beams in inhomogeneous electric fields. Extensive association of the vapors occurs for all but the lighter pentafluorides and the interhalogens. The interhalogen pentafluorides are strongly polar, consistent with the accepted C_4v symmetry. The transition-metal and Group V pentafluorides are all non-polar, except VF₅ and CrF₅ for which temperature-dependent polarity is observed. However, uncertainty exists as to whether these observations are applicable to monomeric pentafluorides in all cases. Mass-spectral cracking patterns are presented for all species.     

Macrodiolide Formation by the Thioesterase of a Modular Polyketide Synthase

Elaiophylin is an unusual C₂‐symmetric antibiotic macrodiolide produced on a bacterial modular polyketide synthase assembly line. To probe the mechanism and selectivity of diolide formation, we sought to reconstitute ring formation in vitro by using a non‐natural substrate. Incubation of recombinant elaiophylin thioesterase/cyclase with a synthetic pentaketide analogue of the presumed monomeric polyketide precursor of elaiophylin, specifically its N‐acetylcysteamine thioester, produced a novel 16‐membered C₂‐symmetric macrodiolide. A linear dimeric thioester is an intermediate in ring formation, which indicates iterative use of the thioesterase active site in ligation and subsequent cyclization. Furthermore, the elaiophylin thioesterase acts on a mixture of pentaketide and tetraketide thioesters to give both the symmetric decaketide diolide and the novel asymmetric hybrid nonaketide diolide. Such thioesterases have potential as tools for the in vitro construction of novel diolides.     

Towards a new framework for evaluating systemic problem structuring methods

Operational researchers and social scientists often make significant claims for the value of systemic problem structuring and other participative methods. However, when they present evidence to support these claims, it is usually based on single case studies of intervention. There have been very few attempts at evaluating across methods and across interventions undertaken by different people. This is because, in any local intervention, contextual factors, the skills of the researcher and the purposes being pursued by stakeholders affect the perceived success or failure of a method. The use of standard criteria for comparing methods is therefore made problematic by the need to consider what is unique in each intervention. So, is it possible to develop a single evaluation approach that can support both locally meaningful evaluations and longer-term comparisons between methods? This paper outlines a methodological framework for the evaluation of systemic problem structuring methods that seeks to do just this.     

The Contribution of the Activation Entropy to the Gas-Phase Stability of Modified Nucleic Acid Duplexes

Tricyclo-DNA (tcDNA) is a sugar-modified analogue of DNA currently tested for the treatment of Duchenne muscular dystrophy in an antisense approach. Tandem mass spectrometry plays a key role in modern medical diagnostics and has become a widespread technique for the structure elucidation and quantification of antisense oligonucleotides. Herein, mechanistic aspects of the fragmentation of tcDNA are discussed, which lay the basis for reliable sequencing and quantification of the antisense oligonucleotide. Excellent selectivity of tcDNA for complementary RNA is demonstrated in direct competition experiments. Moreover, the kinetic stability and fragmentation pattern of matched and mismatched tcDNA heteroduplexes were investigated and compared with non-modified DNA and RNA duplexes. Although the separation of the constituting strands is the entropy-favored fragmentation pathway of all nucleic acid duplexes, it was found to be only a minor pathway of tcDNA duplexes. The modified hybrid duplexes preferentially undergo neutral base loss and backbone cleavage. This difference is due to the low activation entropy for the strand dissociation of modified duplexes that arises from the conformational constraint of the tc-sugar-moiety. The low activation entropy results in a relatively high free activation enthalpy for the dissociation comparable to the free activation enthalpy of the alternative reaction pathway, the release of a nucleobase. The gas-phase behavior of tcDNA duplexes illustrates the impact of the activation entropy on the fragmentation kinetics and suggests that tandem mass spectrometric experiments are not suited to determine the relative stability of different types of nucleic acid duplexes.

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Graphical Abstract ?

     

Sigma/pi Bonding Preferences of Solvated Alkali-Metal Cations to Ditopic Arylmethyl Anions

Arylmethyl anions allow alkali-metals to bind in a σ-fashion to the lateral carbanionic centre or a π-fashion to the aryl ring or in between these extremities, with the trend towards π bonding increasing on descending group 1. Here we review known alkali metal structures of diphenylmethane, fluorene, 2-benzylpyridine and 4-benzylpyridine. Next, we synthesise Li, Na, K monomers of these diarylmethyls using polydentate donors PMDETA or Me₆TREN to remove competing oligomerizing interactions, studying the effect that two aromatic rings has on negative charge (de)localisation via NMR, X-ray crystallographic and DFT studies. Diphenylmethyl and fluorenyl anions maintain C(H)−M interactions regardless of alkali-metal, although the adjacent arene carbons engage in interactions with larger alkali-metals. Introducing a nitrogen atom into the ring (at the 2- or 4-position) encourages relocalisation of negative charge away from the deprotonated carbon and onto nitrogen. Phenyl(2-pyridyl)methyl moves from an enamide formation at one extremity (lithium) to an aza-allyl formation at the other extremity (potassium), while C- or N-coordination modes become energetically viable for Na and K phenyl(4-pyridyl)methyl complexes.     

Collisions of DCl with pure and salty glycerol: enhancement of interfacial D --> H exchange by dissolved NaI

The fate of DCl molecules striking pure glycerol and a 2.6 M NaI-glycerol solution is investigated using scattering, uptake, and residence time measurements. We find that dissolved Na+ and I- ions alter every gas-liquid pathway from the moment of contact of DCl with the surface to its eventual emergence as HCl. In particular, the salt enhances both trapping-desorption of DCl and interfacial DCl --> HCl exchange at the expense of DCl entry into the bulk solution. The reduced entry and enhanced desorption of thermalized DCl molecules are interpreted by assuming that Na+ and I- ions bind to interfacial OH groups and tie up surface sites that would otherwise capture incoming DCl molecules. These ion-glycerol interactions may also be responsible for enhancing interfacial D --> H exchange by disrupting the interfacial hydrogen bond network that carries the newly formed H+ ion away from its Cl- pair. This disruption may increase the fraction of interfacial Cl- and H+ that recombine and desorb immediately as HCl before the ions separate and diffuse deeply into the bulk.     

n-Alkane hydroconversion on Zeogrid and colloidal ZSM-5 assembled from aluminosilicate nanoslabs of MFI framework type

n-Alkane hydroisomerisation and hydrocracking experiments reveal that ZSM-5 materials synthesized by self-assembly of nanoslabs show different molecular shape selectivity than ZSM-5 synthesized by hydrothermal methods.     

Application of Dey–Mittra conformal boundary algorithm to 3D electromagnetic modeling

The Dey–Mittra conformal boundary conditions have been implemented for the finite-difference time-domain (FDTD) electromagnetic solver of the VORPAL plasma simulation framework and studied in the context of three-dimensional, large-scale computations. The maximum stable time step when using these boundary conditions can be arbitrarily small, due to the presence of small fractional cells inside the vacuum region. Use of the Gershgorin Circle theorem allows the determination of a rigorous criterion for exclusion of small cells in order to have numerical stability for particular values of the ratio f_DM≡Δt/Δt_CFL of the time step to the Courant–Friedrichs–Lewy value for the infinite system. Application to a spherical cavity shows that these boundary conditions allow computation of frequencies with second-order error for sufficiently small f_DM. However, for sufficiently fine resolution, dependent on f_DM, the error becomes first order, just like the error for stair-step boundary conditions. Nevertheless, provided one does use a sufficiently small value of f_DM, one can obtain third-order accuracy through Richardson extrapolation. Computations for the TESLA superconducting RF cavity design compare favorably with experimental measurements.     

Kazhdan Constants for the Circle

We calculate the Kazhdan constant for the circle group, withthe whole group as generating set, and we look briefly at theconstants for some smaller generating sets. We show that a certainrestriction of the right regular representation always givesthe Kazhdan constant for a compact abelian group.