New strategies for exploring RNA's 2'-OH expose the importance of solvent during group II intron catalysis

The 2'-hydroxyl group contributes inextricably to the functional behavior of many RNA molecules, fulfilling numerous essential chemical roles. To assess how hydroxyl groups impart functional behavior to RNA, we developed a series of experimental strategies using an array of nucleoside analogs. These strategies provide the means to investigate whether a hydroxyl group influences function directly (via hydrogen bonding or metal ion coordination), indirectly (via space-filling capacity, inductive effects, and sugar conformation), or through interactions with solvent. The nucleoside analogs span a broad range of chemical diversity, such that quantitative structure activity relationships (QSAR) now become possible in the exploration of RNA biology. We employed these strategies to investigate the spliced exons reopening (SER) reaction of the group II intron. Our results suggest that the cleavage site 2'-hydroxyl may mediate an interaction with a water molecule.     

Generation of strong, homochiral bases by electrochemical reduction of phenazine derivatives

Electrochemical reduction of enantiomerically pure amino- and alkoxy-phenazine derivatives forms strongly basic radical anions which give asymmetric induction in the conversion of 3,4-epoxytetrahydrothiophene-1,1-dioxide into the allylic ester with facile regeneration of the phenazine.     

Nuclear hyperfine coupling interactions in the rotational spectra of the linear and bent isomers of HF-N2O

The rotational spectra of six isotopomers of the linear and bent isomers of HF-N₂O have been collected in the 7-18 GHz region with a Fourier transform microwave spectrometer. The nuclear hyperfine structure in the spectra produced by HF spin-spin coupling interaction and nuclear quadrupole coupling interactions due to the D nucleus of DF and the nuclei of N₂O have been resolved and analyzed. In the linear isomer, H in HF is bonded to the terminal N in N₂O. The NF bond lengths are 2.9808(2) Å for the HF-containing isotopomers and 2.9732(2) Å for the DF-containing isotopomers. The zero point angles are 23.1° for HF and 31-34° for N₂O. The hyperfine constants suggest that the HF bond is lengthened by 0.0105 Å upon complexation and that the electric field gradients of the two nitrogen nuclei in N₂O are perturbed differently in the complex. In the bent isomer, the hydrogen bond is formed between HF and O in N₂O. The intermolecular distances are 3.4942(2) Å for the HF-containing isotopomers and 3.4436(2) Å for the DF-containing isotopomers, with HF and N₂O forming angles of 34° and 46°, respectively, with the intermolecular axis. The nuclear quadrupole coupling constants of the two nitrogen nuclei do not indicate electric field gradient perturbation in this isomer.     

Interactive resonant scattering by a cluster of air bubbles in water

An exact, analytical solution is developed for the problem of acoustic-wave scattering from a cluster of ideal, gaseous, spherical bubbles in an unbounded, homogeneous, host fluid. This solution takes into account all modes of oscillation of the bubbles as well as all interactions between them; it is applicable to a wide range of bubble sizes and excitation frequencies. In the low frequency regime, the theory of this paper is shown to reduce to the "monopole" approximation, the effect of higher-order modes being non-negligible only for very small bubble-to-bubble separations. A numerical study of interactive backscattering from small clusters, comprising up to three ideal bubbles, is presented. Interactions between the bubbles are shown to produce downward shifts in the resonance frequency of the cluster, when the scattering configuration is symmetric. Furthermore, asymmetries of the scattering configuration are shown to generate sharp resonances at frequencies above the resonance of the symmetric mode. The results of this paper agree with previous theoretical and experimental work.     

Increasing the crystallisation temperature to access new spin clusters: conversion of [Ni8(cit)6(OH)2(H2O)2]10- to [Ni8(cit)6(OH)2]10-

The role of temperature in the formation of high nuclearity nickel(II) citrate spin clusters is explored, revealing how changes in structure and hence magnetic properties can be triggered through desolvation and ligand reorganisation.     

The selective functionalisation and difunctionalisation of p-substituted calix[6]arene and calix[8]arenes using hydrophilic moieties

Methodologies to access water soluble large ringed calixarenes in good yield using efficient synthetic procedures have been investigated. Symmetrical partial functionalisations at the lower rim are described using activated [n]ethylene glycol chains and the addition behaviour contrasted with that of bromoalkanenitriles which proceeds with no observed regioselectivity. Full functionalisations of the calixarenes bearing hydrophilic groups are then investigated and a two-step procedure established which appears to be generally applicable for the addition of different [n]ethylene glycol chains. Furthermore, difunctionalisation under different reaction conditions are described. Throughout, strategies for the characterisation of these high mass compounds are outlined.     

Addition of dithiols to bis-ynones: development of a versatile platform for the synthesis of polyketide natural products

[reaction: see text] The conjugate addition of dithiols to bis-ynones generates a versatile masked 1,3,5-triketone platform. These functional units are useful intermediates for the synthesis of oxygen-containing heterocycles commonly found in polyketide natural products. The tetrahydropyranyl fragments of the marine macrolides Lyngbouilloside and Callipeltoside A have been synthesized with use of this methodology.     

Quantum impurities and the neutron resonance peak in YBa2Cu3O7: Ni versus Zn

The influence of magnetic (S=1) and nonmagnetic (S=0) impurities on the spin dynamics of an optimally doped high temperature superconductor is compared in YBa2(Cu0.97Ni0.03)3O7 (Tc=80 K) and YBa2(Cu0.99Zn0.01)3O7 (Tc=78 K). In the Ni-substituted system, the magnetic resonance peak (which is observed at Er approximately 40 meV in the pure system) shifts to lower energy with a preserved Er/Tc ratio while the shift is much smaller upon Zn substitution. By contrast Zn, but not Ni, restores significant spin fluctuations around 40 meV in the normal state. These observations are discussed in the light of models proposed for the magnetic resonance peak.     

A general and convenient route to oxazolyl ligands

A diverse range of chiral and achiral oxazolyl ligands, which have many applications including catalysis and luminescent devices, are synthesized simply in three steps from readily available and inexpensive phenol and amino alcohol starting materials. The method can be applied to ligands with electron-donating/-withdrawing and sterically demanding/undemanding substituents, and can conveniently be scaled up to >25 g of product.