Voltammetry and electrocatalytic properties of cobalt (1,4,8,12-tetraazacyclopentadecane) in aqueous solution

Summary The spectrochemical, electrochemical and electrocatalytic properties of Co[15]aneN₄ ([15]aneN₄ = 1,4,8,12-tetraazacyclopentadecane) have been investigated. The results show that, in aqueous solution, this compound mainly exists as three species whose axial coordination positions are occupied by water and/or hydroxy ligands; it is marginal whether other substrates such as Cl^– and NO _inf3 ^sup– interact with the central ion in acid-base solutions. The approximate Pourbaix diagram of Co^III/II[15]ane N₄ was determined. There is an electrochemically-induced isomerization between two trans conformational isomers of the Co[15]aneN₄ complexes in acid and netural solutions. The Co[15]aneN₄ complex has electrocatalytic properties for reduction of nitrate and nitrite only in strong alkaline solution.     

Stereoselective 1,2-cis glycosylation of 2-O-allyl protected thioglycosides

The technique of intramolecular aglycon delivery (IAD), whereby a glycosyl acceptor is temporarily appended to a hydroxyl group of a glycosyl donor is an attractive method that can allow the synthesis of 1,2-cis glycosides in an entirely stereoselective fashion. 2-O-Allyl protected thioglycoside donors are excellent substrates for IAD, and may be glycosylated stereoselectively through a three-step reaction sequence. This sequence consists of quantitative yielding allyl bond isomerisation, to produce vinyl ethers that can then undergo N-iodosuccinimide mediated tethering of the desired glycosyl acceptor, and subsequent intramolecular glycosylation, to yield either alpha-glucosides or beta-mannosides accordingly. Although attempted one-pot tethering and glycosylation is hampered by competitive intermolecular reaction with excess glycosyl acceptor, this problem can be simply overcome by the use of excess glycosyl donor. Allyl mediated IAD is a widely applicable practical alternative to other IAD approaches for the synthesis of beta-mannosides, that is equally applicable for alpha-gluco linkages. It is advantageous in terms of both simplicity of application and yield, and in addition has no requirement for cyclic 4,6-protection of the glycosyl donor.     

Epitaxial film crystallography by high-energy Auger and X-ray photoelectron diffraction

We review recent work in the application of Auger and X-ray photoelectron diffraction at high electron kinetic energies to the problem of structure determination in ultrathin epitaxial overlayers. These closely-related techniques are based on the fact that outgoing Auger and photoelectrons from single-crystal specimens undergo elastic scattering and interference from near-neighbour atoms in the vicinity of the emitter. Such coherent diffraction leads to large intensity modulations as the detected emission direction is varied with respect to the crystal axes of the specimen. The measured modulations are readily interpreted by means of model quantum mechanical scattering calculation in which atomic coordinates in the epitaxial film are systematically varied. Such analyses provide several kinds of useful information, including growth modes accompanying heteroepitaxy, structural details of alloy and compound formation, and quantitative determination of tetragonal distortion at lattice-mismatched heterointerfaces. After a discussion of experimental design and theoretical modelling, we present several case studies of heteroepitaxial growth involving dissimilar materials. In addition, we review the new subfield of Auger and photoelectron holography, and discuss the current state-of-art in both data acquisition and Fourier inversion of experimental data for directly obtaining structural parameters.     

Cholesteric liquid crystal displays as optical sensors of barbiturate binding

The influence on the optical properties of cholesteric liquid crystal displays (LCDs) was examined for neutral molecule binding by mesogen/receptors in the mesomorphic phase. The motivation was to prepare neutral molecule sensors that use a colour change to signal analyte binding. A receptor that binds barbiturate analytes was modified with two or one cholesteryl groups to yield compounds 2 and 3, respectively. LCDs were prepared by incorporating one of the receptor/mesogen compounds into a cholesteric LC blend along with a potential H‐bonding guest. The optical properties of the LCDs were then determined by measuring the absorbance of the displays. For various LCDs, the colour of the display depended upon several factors: the amount of guest molecule used, the number of cholesteryl side chains on the receptor and the mole concentration of receptor/mesogen in the blend. In particular, complementary host/guest binding of H‐bonding analytes by the bis(cholesteryl) receptor 2 in a cholesteric LCD caused a change of up to +70 nm, which was observed by the naked eye as a blue‐to‐orange colour change. Control experiments confirm that the colour of an LCD is a consequence of molecular recognition in the mesomorphic phase.     

A Chemical Probe for Dehydrobutyrine

Bacterial phosphothreonine lyases, or phospholyases, catalyze a unique post‐translational modification that introduces dehydrobutyrine (Dhb) or dehydroalanine (Dha) in place of phosphothreonine or phosphoserine residues, respectively. We report the use of a phospha‐Michael reaction to label proteins and peptides modified with Dha or Dhb. We demonstrate that a nucleophilic phosphine probe is able to modify Dhb‐containing proteins and peptides that were recalcitrant to reaction with thiol or amine nucleophiles under mild aqueous conditions. Furthermore, we used this reaction to detect multiple Dhb‐modified proteins in mammalian cell lysates, including histone H3, a previously unknown target of phospholyases. This method should prove useful for identifying new phospholyase targets, profiling the biomarkers of bacterial infection, and developing enzyme‐mediated strategies for bioorthogonal labeling in living cells.     

Labile coodination dendrimers

Addition of anionic benzylsulfate dendrons to dynamic mixtures of Ag+ and triphosphine ligands results in the assembly of loosely-bonded cage-core dendrimers.     

Reactions involving fluoride ion. Part 40. Amines as initiators of fluoride ion catalysed reactions

Tetrakis(dimethylamino)ethene (TDAE) and trimethylamine react with anhydrous unsaturated fluorocarbons to produce, ‘in situ’, powerful fluoride- ion sources. These are used to initiate carbon- carbon bond forming reactions eg. oligomerisation and polyfluoroalkylation, and many of these reactions occur efficiently in the absence of a solvent.     

A comparative study of single crystal magnesium oxide and oxidised magnesium by auger electron spectroscopy

In a study by AES of the surfaces of single crystal magnesium oxide and magnesium after various stages of oxidation, it has been shown that Auger energy shifts are produced by surface charging. Recognition of the charging effects has enabled the peak in the low energy spectrum of magnesium oxide crystal to be assigned. The low energy secondary electron spectra of both MgO crystal and oxidised magnesium are complicated by the presence of extra features which arise from diffraction of true secondary electrons, and in particular for oxidised magnesium a cross-transition occurring at the metal-oxide interface. Oxidation studies of sodium also reveal transitions arising from a similar process.     

Low energy Auger and loss electron spectra from magnesium and its oxide

Data have been obtained from Auger and energy loss processes in clean metallic Mg, Mg during stages of oxidation, and UHV cleaved MgO(100) surfaces. Particular attention has been paid to twenty features below 200 eV in the Auger spectra from these surfaces. A comparison of spectra from the metal, oxidised metal surface, and single crystal MgO has enabled estimates to be made of surface charging effects, and the MgO steady state surface potential is found to be near + 10 V above ground. All the Auger features are given assignments, two of which are interfacial processes involving ionic initial states and metallic final states. Several features in the low energy Auger spectrum are attributed to diffraction of true secondary electrons.