Enhanced UV photosensing properties of ZnO nanowires prepared by electrodeposition and atomic layer deposition

A new process enabling the synthesis of zinc oxide (ZnO) and Al-doped ZnO nanowires (NWs) for photosensing applications is reported. By combining atomic layer deposition (ALD) for the seed layer preparation and electrodeposition for the NW growth, high-quality ZnO nanomaterials were prepared and tested as ultraviolet (UV) sensors. The obtained NWs are grown as arrays perpendicular to the substrate surface and present diameters between 70 and 130 nm depending on the Al doping, as seen from scanning electron microscopy (SEM) studies. Their hexagonal microstructure has been determined using X-ray diffraction and Raman spectroscopy. An excellent performance in UV sensing has been observed for the ZnO NWs with low Al doping, and a maximal photoresponse current of 11.1 mA has been measured. In addition, initial studies on the stability have shown that the NW photoresponse currents are stable, even after ten UV on/off cycles.     

Curve graphs and Garside groups

We present a simple construction which associates to every Garside group a metric space, called the additional length graph, on which the group acts. These spaces share important features with curve graphs: they are \(\delta \)-hyperbolic, infinite, and typically locally infinite graphs. We conjecture that, apart from obvious counterexamples, additional length graphs have always infinite diameter. We prove this conjecture for the classical example of braid groups \((B_n,B_n^{+},\varDelta )\); moreover, in this framework, reducible and periodic braids act elliptically, and at least some pseudo-Anosov braids act loxodromically. We conjecture that for \(B_n\), the additional length graph is actually quasi-isometric to the curve graph of the n times punctured disk.     

Selectivity among two lectins: probing the effect of topology, multivalency and flexibility of "clicked" multivalent glycoclusters

The design of multivalent glycoconjugates has been developed over the past decades to obtain high-affinity ligands for lectin receptors. While multivalency frequently increases the affinity of a ligand for its lectin through the so-called "glycoside cluster effect", the binding profiles towards different lectins have been much less investigated. We have designed a series of multivalent galactosylated glycoconjugates and studied their binding properties towards two lectins, from plant and bacterial origins, to determine their potential selectivity. The synthesis was achieved through copper(I)-catalysed azide-alkyne cycloaddition (CuAAC) under microwave activation between propargylated multivalent scaffolds and an azido-functionalised carbohydrate derivative. The interactions of two galactose-binding lectins from Pseudomonas aeruginosa (PA-IL) and Erythrina cristagalli (ECA) with the synthesized glycoclusters were studied by hemagglutination inhibition assays (HIA), surface plasmon resonance (SPR) and isothermal titration microcalorimetry (ITC). The results obtained illustrate the influence of the scaffold's geometry on the affinity towards the lectin and also on the relative potency in comparison with a monovalent galactoside reference probe.     

Nonribosomal peptide synthesis in animals: the cyclodipeptide synthase of Nematostella

Cyclodipeptide synthases (CDPSs) are small enzymes structurally related to class-I aminoacyl-tRNA synthetases (aaRSs). They divert aminoacylated tRNAs from their canonical role in ribosomal protein synthesis, for cyclodipeptide formation. All the CDPSs experimentally characterized to date are?bacterial. We show here that a predicted CDPS from the sea anemone Nematostella vectensis is an active CDPS catalyzing the formation of various cyclodipeptides, preferentially containing tryptophan. Our findings demonstrate that eukaryotes encode active CDPSs and suggest that all CDPSs have?a similar aminoacyl-tRNA synthetase-like architecture and ping-pong mechanism. They also raise questions about the biological roles of the cyclodipeptides produced in bacteria and eukaryotes.     

Highly enantioselective and regioselective copper-catalyzed 1,4 addition of grignard reagents to cyclic enynones

In this letter we describe an unusual result in terms of regioselectivity with respect to copper-catalyzed conjugate additions of various Grignard reagents to cyclic enynones. The use of Cu(OTf)(2) and NHC ligand L1 as the catalyst combination in CH(2)Cl(2) led to the unique formation of the 1,4 adduct. This selectivity does not follow the general trend previously observed in the literature using extended Michael acceptors. Moreover these reactions allowed for the creation of a quarternary stereogenic center with enantioselectivities up to 97% ee.     

Enantioselective supramolecular catalysis induced by remote chiral diols

A new method of creating libraries of chiral diphosphines is presented. Supramolecular coordination compounds based on Ti, Rh, achiral ditopic ligands, and chiral diols were synthesized by in situ mixing and used as catalysts in the asymmetric hydrogenation of (Z)-methyl 2-acetamido-3-phenylacrylate, giving ee's of up to 92%. The ditopic ligands contain a Schiff base that coordinates to the assembly metal Ti and a phosphine as a ligand for Rh. Chirality is introduced by coordination of the chiral diols to Ti. The controlling chiral center and the substrate are separated by as much as 13 ?.     

Inhomogeneous fluids of colloidal hard dumbbells: fundamental measure theory and Monte Carlo simulations

Recently, a density functional theory for hard particles with shape anisotropy was developed, the extended deconvolution fundamental measure theory (edFMT). We apply edFMT to hard dumbbells, arguably the simplest non-convex shape and readily available experimentally in the form of colloids. We obtain good agreement between edFMT and Monte Carlo simulations for fluids of dumbbells in a slit and for the same system under gravity. This indicates that edFMT can be successfully applied to nearly all colloidal shapes, not just for the convex shapes for which edFMT was originally derived. A theory, such as edFMT, that allows a fast and general way of mapping the phase behavior of anisotropic colloids, can act as a useful guide for the design of colloidal shapes for various applications.     

Phase behavior of hard colloidal platelets using free energy calculations

We investigate the phase behavior of a model for colloidal hard platelets and rigid discotic molecules: oblate hard spherocylinders (OHSC). We perform free energy calculations using Monte Carlo simulations to map out the phase diagram as a function of the aspect ratio L∕D of the particles. The phase diagram displays a stable isotropic phase, a nematic liquid crystal phase for L∕D≤0.12, a columnar phase for L∕D?0.3, a tilted crystal phase for L?0.45, and an aligned crystal phase for L∕D?0.45. We compare the results to the known phase diagram of hard cut spheres. Thin cut spheres are almost cylinder-shaped, while the interactions between real discotic mesogens and colloidal platelets are more consistent with the toroidal rims of the OHSC. Since the shapes of the OHSC and the cut spheres are otherwise similar, the phase diagrams of the two types of particles are quite akin. However, the tilted crystal phase for OHSC, which is of a crystal type that is frequently found in experiments on disklike molecules, has not been found for hard cut spheres. Furthermore, although we have found a cubatic phase, it was shown to be definitely unstable, whereas the stability of the cubatic phase of cut spheres is still disputed. Finally, we also show that the phase boundaries differ significantly from those for cut spheres. These are remarkable consequences of a subtle change in particle shape, which show that for a detailed comparison with the phase behavior of experimental particles, the OHSC should be used as a model particle.     

Organogel formation rationalized by Hansen solubility parameters

Some organic compounds gelate particular solvents by forming a network of anisotropic fibres. We show that Hansen solubility parameters can be used to predict the range of solvents that are likely to be gelled by any given gelator.