Structure of ethylene sulphide crystallites in block copolymers

Block copolymers, having the configuration ethylene sulphide-isoprene-styrene or ethylene sulphide-isoprene-ethylene sulphide, have been characterized to define the structure of the ethylene sulphide moiety. It is concluded that ethylene sulphide-isoprene-styrene block copolymers exist in solution and in bulk (above the styrene softening point) as radial aggregates held together by polyethylene sulphide crystallites. During polymerization, these crystallites are formed with a linear extended chain morphology which is retained in bulk in ethylene sulphide-isoprene-styrene copolymers: in the copolymers which require processing above the melting point of the ethylene sulphide crystallites, the linear morphology is destroyed during moulding.     

The analysis of thyroxine in human serum by an 'exact matching' isotope dilution method with liquid chromatography/tandem mass spectrometry

A method for the analysis of thyroxine in human serum, utilising 'exact matching' isotope dilution mass spectrometry (IDMS) in combination with liquid chromatography/tandem mass spectrometry (LC/MS/MS), has been developed with a limit of quantification of 0.5 ng g(-1) of thyroxine in human serum. The extraction and clean-up of thyroxine from serum involves an efficient protein-precipitation stage followed by a solid-phase extraction procedure to produce an extract essentially free from interfering compounds. The method is reproducible, with expanded uncertainties of less than 2%, and is relatively fast to perform.     

The stereochemical course of bromoetherification of enynes

Enynes undergo stereoselective syn intramolecular bromoetherification; the stereochemical course of the reaction was elucidated by X-ray crystallographic studies and by stereospecific synthesis of authentic bromoallenes.     

Highly sensitive detection of dye-labelled DNA using nanostructured gold surfaces

Careful control of surface chemistry results in strong surface enhanced resonance Raman scattering from dye-labelled oligonucleotides assembled on nanostructured gold surfaces, releasing their potential as reliable enhancing surfaces.     

Photoelectron spectroscopy of the parent anions of the nucleotides, adenosine-5'-monophosphate and 2'deoxyadenosine-5'-monophosphate

The parent anions of the nucleotides, adenosine-5(')-monophosphate (AMPH) and 2(')deoxyadenosine-5(')-monophosphate (dAMPH) were generated in a novel source and their photoelectron spectra recorded with 3.49 eV photons. Vertical detachment energy (VDE) and the adiabatic electron affinity (EA(a)) values were extracted from each of the two spectra. Concurrently, Kobylecka et al. [J. Chem. Phys. 128, 044315 (2008)] conducted calculations which explored electron attachment to dAMPH. Based on the agreement between their calculated and our measured VDE and EA(a) values, we conclude that the dAMPH(-) anions studied in these experiments were formed by electron-induced, intramolecular, (barrier-free) proton-transfer as predicted by the calculations. Given the similarities between the photoelectron spectra of dAMPH(-) and AMPH(-), it is likely that AMPH(-) can be described in the same manner.     

Constellations and their relationship with categories

Constellations are partial algebras that are one-sided generalisations of categories. Indeed, we show that a category is exactly a constellation that also satisfies the left-right dual axioms. Constellations have previously appeared in the context of inductive constellations: the category of inductive constellations is known to be isomorphic to the category of left restriction semigroups. Here we consider constellations in full generality, giving many examples. We characterise those small constellations that are isomorphic to constellations of partial functions. We examine in detail the relationship between constellations and categories. In particular, we characterise those constellations that arise as (sub-)reducts of categories. We demonstrate that the notion of substructure can be captured within constellations but not within categories. We show that every constellation P gives rise to a category \({\mathcal{C}(P)}\), its canonical extension, in a simplest possible way, and that P is a quotient of \({\mathcal{C}(P)}\) in a natural sense. We also show that many of the most common concrete categories may be constructed from simpler quotient constellations using this construction. We characterise the canonical congruences \({\delta}\) on a given category \({K}\) (those for which \({K \cong \mathcal{C}(K/\delta))}\), and show that the category of constellations is equivalent to the category of \({\delta}\)-categories, that is, categories equipped with distinguished canonical congruence \({\delta}\).The main observation of this paper is that category theory as it applies to the familiar concrete categories of modern mathematics (which come equipped with natural notions of substructures and indeed are \({\delta}\)-categories) may be subsumed by constellation theory.     

Synthesis of a novel polycyclic ring scaffold with antimitotic properties via a selective domino Heck–Suzuki reaction

The synthesis of a previously undescribed sp³-rich 6-5-5-6 tetracyclic ring scaffold using a palladium catalysed domino Heck–Suzuki reaction is reported. This reaction is high-yielding, selective for the domino process over the direct Suzuki reaction and tolerant towards a variety of boronic acids. The novel scaffold can also be accessed via domino Heck–Stille and radical cyclisations. Compounds based around this scaffold were found to be effective antimitotic agents in a human cancer cell line. Detailed phenotypic profiling showed that the compounds affected the congression of chromosomes to give mitotic arrest and apoptotic cell death. Thus, a novel structural class of antimitotic agents that does not disrupt the tubulin network has been identified.     

The feasibility of using fluorescence spectroscopy as a rapid, non-invasive method for evaluating sunscreen performance

We have carried out ex vivo studies to examine the feasibility of using fluorescence spectroscopy as an in vivo quantitative technique to assess sunscreen substantivity in terms of skin surface thickness and/or photoprotection. We found that the majority of sunscreens produced insufficient natural fluorescence and so we have attempted to increase the fluorescent signal by adding various fluorescing agents to the sunscreens. However, none of these substances is ideal; either they do not bind sufficiently strongly to sunscreen products, or their fluorescence is quenched by the active ingredients contained within sunscreens. The feasibility of using fluorescence spectroscopy for in vivo quantitative assessments of sunscreen substantivity therefore remains unproved and is dependent on a suitable fluorescent agent being found. Such an agent would have to be non-toxic, mix readily with sunscreens and be excited by visible wavelengths.     

Rearrangements in Allylpalladium Complexes with Hemilabile Chelating Ligands

In addition to η³‐ to η¹‐allyl rearrangement, η²‐ to η¹‐chelating‐ligand rearrangements can affect the dynamic properties in allylpalladium complexes containing hemilabile ligands. These rearrangements have the potential of altering stereochemistry, which can ultimately affect the stereochemistry and regiochemistry of reactions upon the allyl group, e.g., allylic alkylation. Apparent rotation of an η³‐allyl in four‐coordinate Pd^II‐complexes can be the result of ligand exchange or intramolecular processes. NMR Studies indicate that the effects of η²‐ to η¹‐chelating‐ligand stereochemistry and rearrangements may be hidden or subtle, and both intra‐ and intermolecular processes may be important.     

Microarray sampling-platform fabrication using bubble-jet technology for a biochip system

The fabrication of microarrays containing PCR-amplified genomic DNA extracts from mice tumors on a Zetaprobe membrane using a modified thermal ink-jet printer is described. A simple and cost-effective procedure for the fabrication of microarrays containing biological samples using a modified bubble-jet printing system is presented. Because of their mass-produced design, ink-jet printers are a much cheaper alternative to conventional spotting techniques. The usefulness of the biochip microarray platform is illustrated by the detection of human fragile histidine triad (FHIT), a tumor suppressor gene. Subcutaneous carcinomas were induced with MKN/FHIT and MKN/E4 cell lines in immunodeficient mice. Several weeks into their development, the tumors from both groups of mice were removed and subjected to DNA extraction by lysis of tissue samples. The extracted DNA samples were amplified by PCR (30 cycles) using the primers corresponding to nucleotides 2 to 18 of the FHIT sequence. The resulting solution was transferred to the individual reservoirs of a three-color cartridge from a conventional thermal ink-jet printer (HP 694C), and arrays were printed on to a Zetaprobe membrane. After spotting, these membranes were used in a hybridization assay, using fluorescent probes, and detected with a biochip.