Synthesis and Properties of 2,3-Diethynyl-1,3-Butadienes

The first general preparative access to compounds of the 2,3-diethynyl-1,3-butadiene (DEBD) class is reported. The synthesis involves a one-pot, twofold Sonogashira-type, Pd⁰-catalyzed coupling of two terminal alkynes and a carbonate derivative of a 2-butyne-1,4-diol. The synthesis is broad in scope and members of this structural family are kinetically stable enough to be handled using standard laboratory techniques at ambient temperature. They decompose primarily through heat-promoted cyclodimerizations, which are impeded by alkyl substitution and accelerated by aryl or alkenyl substitution. An iterative sequence of these unprecedented Sonogashira-type couplings generates a new type of expanded dendralene. A suitably substituted DEBD carrying two terminal alkyne groups undergoes Glaser–Eglinton cyclo-oligomerization to produce a new class of expanded radialenes, which are chiral due to restricted rotation about their 1,3-butadiene units. The structural features giving rise to atropisomerism in these compounds are distinct from those reported previously.     

210Po in the environment: insight into the naturally occurring polonium isotope

Journal of Radioanalytical and Nuclear Chemistry - Polonium is rapidly emerging as an international environmental health concern primarily because of the recent rise in hydraulic fracturing...     

Hierarchical visual data mining for large-scale data

Summary  An increasingly important problem in exploratory data analysis and visualization is that of scale; more and more data sets are much too large to analyze using traditional techniques, either in terms of the number of variables or the number of records. One approach to addressing this problem is the development and use of multiresolution strategies, where we represent the data at different levels of abstraction or detail through aggregation and summarization. In this paper we present an overview of our recent and current activities in the development of a multiresolution exploratory visualization environment for large-scale multivariate data. We have developed visualization, interaction, and data management techniques for effectively dealing with data sets that contain millions of records and/or hundreds of dimensions, and propose methods for applying similar approaches to extend the system to handle nominal as well as ordinal data.     

Geometrical forms of Abelès'' equations involving film thickness

Abelès' equations (in terms of ₁; ₂ and optical film thickness x) for all the eight optical functions (R_s; R_p; T_s; T_p; F_s; F_p; X_s and X_p) have been expressed in the form of equations representing standard geometrical three-dimensional figures. X_s and X_p are represented by plane surfaces whilst the remainder are skew cones. Translated into the n; k notation; X_s and X_p generate hyperboloids whilst the remainder produce paraboloids whose cross-sections are parts of figures of eight.     

Metastable Dynamics and Spatially Inhomogeneous Equilibria in Dumbbell-Shaped Domains

The motion of internal layers for three singularly perturbed reaction diffusion problems, including the Allen–Cahn equation, is studied in a two-dimensional dumbbell-shaped domain. The channel region that connects the two attachments, or lobes, of the dumbbell is taken to be rectangular. The motion of straight-line internal layers in the channel region is analyzed by using an asymptotic projection method. It is shown that this motion is metastable and highly dependent on the local convexity properties of the boundary near the contact region between the ends of the channel and the two attachments. When the domain is nonconvex it is shown that the metastable internal layers dynamics in the channel tends, as t →∞, to a limiting, stable, spatially inhomogeneous equilibrium solution.     

BMO from dyadic BMO via expectations on product spaces of homogeneous type

Using the random dyadic lattices developed by Hytönen and Kairema, we build up a bridge between BMO and dyadic BMO, and hence one between VMO and dyadic VMO, via expectations over dyadic lattices on spaces of homogeneous type, including both the one-parameter and product cases. We also obtain a similar relationship between _Ap$A_p$ and dyadic _Ap$A_p$, as well as one between the reverse Hölder class _RHp${\mathit{RH}}_p$ and dyadic _RHp${\mathit{RH}}_p$, via geometric–arithmetic expectations. These results extend the earlier theory along this line, developed by Garnett, Jones, Pipher, Ward, Xiao and Treil, to the more general setting of spaces of homogeneous type in the sense of Coifman and Weiss.     

Submicron streptavidin patterns for protein assembly

Micron and submicron-scale features of aldehyde functionality were fabricated in polymer films by photolithography to develop a platform for protein immobilization and assembly at a biologically relevant scale. Films containing the pH-reactive polymer poly(3,3'-diethoxypropyl methacrylate) and a photoacid generator (PAG) were patterned from 500 nm to 40 mum by exposure to 365 nm (i-line) light. Upon PAG activation and hydrolysis of acetals, aldehyde groups formed. After the films were incubated with a biotinylated aldehyde reactive probe, the X-ray photoelectron spectroscopy results were consistent with biotin being attached to the surface. The background was subsequently passivated by flood exposure and incubation with an aminooxy-terminated poly(ethylene glycol), resulting in a 98% reduction in nonspecific protein adsorption. Protein patterning and assembly was demonstrated using streptavidin, biotinylated anthrax toxin receptor-1, and the protective antigen moiety of anthrax toxin and confirmed by fluorescence microscopy and atomic force microscopy (AFM). AFM demonstrated that 500 nm protein features were achieved. Because of the abundance of biotinylated proteins, this methodology provides a platform for protein immobilization and assembly for various applications in biotechnology.     

Polynuclear lanthanide complexes of a series of bridging ligands containing two tridentate N,N',O-donor units: structures and luminescence properties

A set of three potentially bridging ligands containing two tridentate chelating N,N',O-donor (pyrazole-pyridine-amide) donors separated by an o, m, or p-phenylene spacer has been prepared and their coordination chemistry with lanthanide(III) ions investigated. Ligand L(1) (p-phenylene spacer) forms complexes with a 2:3 M:L ratio according to the proportions used in the reaction mixture; the Ln(2)(L(1))(3) complexes contain two 9-coordinate Ln(III) centres with all three bridging ligands spanning both metal ions, and have a cylindrical (non-helical) 'mesocate' architecture. The 1:1 complexes display a range of structural types depending on the conditions used, including a cyclic Ln(4)(L(1))(4) tetranuclear helicate, a Ln(2)(L(1))(2) dinuclear mesocate, and an infinite one-dimensional coordination polymer in which metal ions and bridging ligands alternate along the sequence. ESMS studies indicate that the 1:1 complexes form a mixture of oligonuclear species {Ln(L(1))}(n) in solution (n up to 5) which are likely to be cyclic helicates. In contrast, ligands L(2) and L(3) (with o- and m-phenylene spacers, respectively) generally form dinuclear Ln(2)L(2) Ln(III) complexes in which the two ligands may be arranged in a helical or non-helical architecture about the two metal ions. These complexes also contain an additional exogenous bidentate bridging ligand, either acetate or formate, which has arisen from hydrolysis of solvent molecules promoted by the Lewis-acidity of the Ln(III) ions. Luminescence studies on some of the Nd(III) complexes showed that excitation into ligand-centred pi-pi* transitions result in the characteristic near-infrared luminescence from Nd(III) at 1060 nm.     

Dipyrrinone imines: controlling self-association

We report the synthesis of three new dipyrrinone imine analogues and the characterisation of their self-association properties. Based on vapour pressure osmometry and nuclear magnetic resonance studies, placing the imine functional group at C(9) of the dipyrrinone disrupts the native self-association of the dipyrrinone core in a manner that correlates with the conformational A-value of the imine N-substituent.     

Reorientation dynamics of nanoconfined water: power-law decay, hydrogen-bond jumps, and test of a two-state model

The reorientation dynamics of water confined within nanoscale, hydrophilic silica pores are investigated using molecular dynamics simulations. The effect of surface hydrogen-bonding and electrostatic interactions are examined by comparing with both a silica pore with no charges (representing hydrophobic confinement) and bulk water. The OH reorientation in water is found to slow significantly in hydrophilic confinement compared to bulk water, and is well-described by a power-law decay extending beyond one nanosecond. In contrast, the dynamics of water in the hydrophobic pore are more modestly affected. A two-state model, commonly used to interpret confined liquid properties, is tested by analysis of the position-dependence of the water dynamics. While the two-state model provides a good fit of the orientational decay, our molecular-level analysis evidences that it relies on an over-simplified picture of water dynamics. In contrast with the two-state model assumptions, the interface dynamics is markedly heterogeneous, especially in the hydrophilic pore and there is no single interfacial state with a common dynamics.