Gel- and Solid-State-Structure of Dialanine and Diphenylalanine Amphiphiles: Importance of C⋅⋅⋅H Interactions in Gelation

To investigate the role of the capping group in the solution and solid-state self-assembly of short peptide amphiphiles, dialanine and diphenylalanine have been linked via the N-terminus to a benzene (phenyl) and 3-naphthyl capping groups using three different methylene linkers; (CH₂)_n, n=0–4 for the benezene and 0, 1 and 2 for the naphthalene capping group. Atomic force microscopy (AFM), oscillatory rheology, circular dichroism (CD), and IR analysis have been employed to understand the properties of these peptide-based hydrogels. Several X-ray structures of these short peptide gelators give useful conformational information regarding packing. A comparison of these solid state structures with their gel state properties yielded greater insights into the process of self-assembly in short peptide gelators, particularly in terms of the important role of C⋅⋅⋅H interactions appear to play in determining if a short aromatic peptide does form a gel or not.     

Optical stimulation of neural tissue in vivo

For more than a century, the traditional method of stimulating neural activity has been based on electrical methods, and it remains the gold standard to date. We report a technological breakthrough in neural activation in which low-level, pulsed infrared laser light is used to elicit compound nerve and muscle potentials in mammalian peripheral nerve in vivo. Optically induced neural action potentials are spatially precise, artifact free, and damage free and are generated by use of energies well below tissue ablation threshold. Thus optical stimulation presents a simple yet novel approach to contact-free in vivo neural activation that has major implications for clinical neurosurgery, basic neurophysiology, and neuroscience.     

Detecting DNA methylation through changes in transverse proton relaxation

We present a facile, simple method to detect DNA methylation by measuring the transverse proton relaxation behaviour. Positively charged nanoparticles are arranged along the negatively charged backbone of DNA strands through electrostatic interactions. The arrangement of NPs along DNA strands aids to amplify and compare the transverse proton relaxation signal for un-cut versus cut DNA strands cleaved by sequence specific restriction enzymes. Results from this study suggest that the presence of methylation on DNA can be detected using superparamagnetic NPs using NMR.     

The mechanism responsible for extraordinary Cs ion selectivity in crystalline silicotitanate

Combining information from time-resolved X-ray and neutron scattering with theoretical calculations has revealed the elegant mechanism whereby hydrogen crystalline silicotitanate (H-CST; H2Ti2SiO7 x 1.5 H2O) achieves its remarkable ion-exchange selectivity for cesium. Rather than a simple ion-for-ion displacement reaction into favorable sites, which has been suggested by static structural studies of ion-exchanged variants of CST, Cs(+) exchange proceeds via a two-step process mediated by conformational changes in the framework. Similar to the case of ion channels in proteins, occupancy of the most favorable site does not occur until the first lever, cooperative repulsive interactions between water and the initial Cs-exchange site, repels a hydrogen lever on the silicotitanate framework. Here we show that these interactions induce a subtle conformational rearrangement in CST that unlocks the preferred Cs site and increases the overall capacity and selectivity for ion exchange.     

Uranyl-specific binding at a functionalised interface: a chemophotonic fibre optic sensor platform

Detection of radiological materials in the solution phase is restricted by conventional radiation-counting techniques owing to extreme attenuation. Chemical sensing of the resultant radiological species such as uranyl UO(2)(2+) is possible on the surface of a plastic or glass fibre optic. A dihydroxy isoamethryin complex is tethered to the fibre surface which has a large extinction coefficient (119 000 M(-1) cm(-1) at lambda = 439 nm) and changes colour upon binding UO(2)(2+). The spectral changes are greater on the surface than in solution and binding is specific to UO(2)(2+) with small interferences from Gd(3+). Monitoring the spectral response in three detector bands in the red, green and blue enable the optical power change to be measured with sensitivities of 1 mdB, allowing UO(2)(2+) to be detected confidently at 50-100 ppb levels. Real-time kinetic analysis enables discrimination between the target species and possible interferents.     

Toposes for semigroups: an invitation

This is an expository paper in which we explain the basic ideas of topos theory in connection with semigroup theory. We focus mainly on the classifying topos of an inverse semigroup or pseudogroup, and to some extent on creating a dictionary between the language of semigroups and topos theory. We begin with the algebraic theory having to do with inverse semigroups, and then turn to an analysis of pseudogroups using sheaf theory. Our work includes some new material on wide semigroup homomorphisms and their geometric morphisms.

     

Pentameric circular iron(II) double helicates and a molecular pentafoil knot

We report on the synthesis of 11 pentameric cyclic helicates formed by imine condensation of alkyl monoamines with a common bis(formylpyridine)bipyridyl-derived building block and iron(II) and chloride ions. The cyclic double-stranded helicates were characterized by NMR spectroscopy, mass spectrometry, and in the case of a 2,4-dimethoxybenzylamine-derived pentameric cyclic helicate, X-ray crystallography. The factors influencing the assembly process (reactant stoichiometry, concentration, solvent, nature and amount of anion) were studied in detail: the role of chloride in the assembly process appears not to be limited to that of a simple template, and larger circular helicates observed with related tris(bipyridine) ligands with different iron salts are not produced with the imine ligands. Using certain chiral amines, pentameric cyclic helices of single handedness could be isolated and the stereochemistry of the helix determined by circular dichroism. By employing a particular diamine, a closed-loop molecular pentafoil knot was prepared. The pentafoil knot was characterized by NMR spectroscopy, mass spectrometry, and X-ray crystallography, confirming the topology and providing insights into the reasons for its formation.     

Polydopamine as a Visible-Light Photosensitiser for Photoinitiated Polymerisation

Polydopamine (PDA) is a synthetic model for melanin and has a wide range of opto-electronic properties that underpin its utility in applied and biological settings, from broadband light absorbance to possessing stable free radical species. Here, we show that PDA free radicals are photo-responsive under visible light irradiation, enabling PDA to serve as a photo-redox catalyst. Steady-state and transient electron spin resonance spectroscopy reveals a reversible amplification in semiquinone radical population within PDA under visible light. This photo-response modifies the redox potential of PDA and supports sensitisation of exogenous species via photoinduced electron transfer (PET). We demonstrate the utility of this discovery by employing PDA nanoparticles to photosensitise a common diaryliodonium photoinitiator and initiate free-radical polymerisation (FRP) of vinylic monomers. In situ ¹H nuclear magnetic resonance spectroscopy reveals an interplay between PDA-driven photosensitising and radical quenching during FRP under blue, green, and red light. This work provides crucial insights into the photoactive free radical properties of melanin-like materials and reveals a promising new application for polydopamine as a photosensitiser.     

Soluble polymeric ligands for metal complexation and catalyst recovery

Soluble polymers that bind metals and that in turn can be separated from other components of a reaction mixture are described. The polymers used include derivatives of acrylamides, acrylates, polystyrene and other polymers. Both sequestration of trace metals and recovery of homogeneous catalysts is discussed. Separation methods using liquid/liquid mixtures that are monophasic during a reaction but biphasic during a separation are emphasized.