Influence of Ions on Aqueous Acid–Base Reactions

We study the effects of bromide salts on the rate and mechanism of the aqueous proton/deuteron‐transfer reaction between the photoacid 8‐hydroxy‐1,3,6‐pyrenetrisulfonic acid (HPTS) and the base acetate. The proton/deuteron release is triggered by exciting HPTS with 400 nm femtosecond laser pulses. Probing the electronic and vibrational resonances of the photoacid, the conjugate photobase, the hydrated proton/deuteron and the accepting base with femtosecond visible and mid‐infrared pulses monitors the proton transfer. Two reaction channels are identified: 1) direct long‐range proton transfer over hydrogen‐bonded water bridges that connect the acid and base and 2) acid dissociation to produce fully solvated protons followed by proton scavenging from solution by acetate. We observe that the addition of salt affects the long‐range reaction pathway, and reduces both the rate at which protons are released to solution by HPTS and the rate at which solvated protons are scavenged from solution by acetate. We study the dependence of these effects on the nature and concentration of the dissolved salt.     

Salmonella surveillance in Australia--created from adversity

A national scheme of Salmonella surveillance emerged in Australia as a direct result of high-profile outbreaks in 1977. A typing laboratory in Victoria put together a working model using the computer technology available at the time. The evolving information-gathering system has stood the test of time and has provided an invaluable bank of information covering isolations from humans and other sources. The databases have been used effectively in detecting trends and outbreaks and have assisted in the solution of public health problems--even extending internationally. The way in which this has been done and the lessons learned are described.     

Dramatic Effect of Magnetite Particles on the Dynamics of Photogenerated Free Radicals

Abstract— Polymeric particles of about 1 u.m in diameter and containing around 40% magnetite have a dramatic influence on the dynamics of triplet radical pair reactions occurring in micelles in their vicinity. The effect has been monitored with laser flash photolysis techniques and results in a decrease of the number of radicals that separate from their geminate partner and an acceleration of radical pair geminate reactions. The effect involves remote interactions because the solution contains ca 10¹¹micelles for each polymeric particle. Magnetite also perturbs the way in which the radicals interact with an external magnetic field.     

Identification and characterization of monoanionic tripodal tetradentate ligand complexes of copper(I) and copper(II) involved in halogen atom transfer reactions

The copper(I) complex of bis-(2-(2-pyridyl)-ethyl)-(2-(N-p-toluenesulfonamido)-ethyl)amine (PETAEA), a monoanionic, tripodal tetradentate ligand, was prepared, characterized, and shown to be an effective catalyst for atom transfer radical polymerization (ATRP). A model atom transfer reaction of Cu(PETAEA) with 1-phenylethyl bromide and TEMPO radical trapping agent was studied. The copper(II) complex formed in this reaction was identified by comparison of its spectroscopic data with that of Cu(PETAEA)Br prepared by an independent synthesis. Kinetic and spectroscopic data indicated that the reaction mechanism involved simple atom transfer from the alkyl halide to the Cu(PETAEA) to form the Cu(PETAEA)Br, and no other intermediates were involved. The solid-state structures of the copper(I) and (II) complexes appeared to be maintained in solution, so this system is an atom transfer reaction in which all of the reactive species are identified and characterized.     

Determination of dissociation constants for a heparin-binding domain of amyloid precursor protein and heparins or heparan sulfate by affinity capillary electrophoresis

Dynamic affinity capillary electrophoresis (ACE) was used for determining the binding constants between heparin-like glycosaminoglycans and the (96-110) heparin-binding domain of amyloid precursor protein (APP). The migration time shift of the (96-110) APP peptide was monitored as the concentration of heparin was increased in the background electrolyte. The compounds investigated included low-molecular-weight heparin, porcine mucosa heparin, and heparan sulfate. Change in mobility as a function of glycosaminoglycan concentration was plotted using both linear regression (Scatchard analysis) and nonlinear regression. Dissociation constants (K(d)) were determined and compared for both sets of analyses with the low-molecular-weight heparin giving the most reproducible results and best fit with a K(d) value of 3.9 microM.     

Quantized double-layer charging of highly monodisperse metal nanoparticles

We describe unprecedented resolution of electrochemically observed quantized double layer (QDL) charging, attained with use of reduced solution temperatures and with an annealing procedure that produces hexanethiolate monolayer protected gold clusters (C6 MPCs) with a high level of monodispersity in charging capacitance, C(CLU). The spacing DeltaV = e/C(CLU) on the electrochemical potential axis between one electron changes in the electronic charge of nanoscopic metal particles is determined by their effective capacitance C(CLU). The high monodispersity of the C6 MPCs with Au(140) cores facilitates (a) detailed rotated disk and cyclic voltammetric measurements, (b) simulation of QDL waveshapes based on assumed reversible, multivalent redox-like behavior, (c) determination of nanoparticle diffusion rates, and (d) observation of as many as 13 changes in the MPC charge state, from MPC(6-) to MPC(7+). The single electron QDL charging peaks are quite evenly spaced (DeltaV constant) at potentials near the MPC potential of zero charge, but are irregularly spaced at more positive and negative potentials. The irregular spacing is difficult to rationalize with classical double layer capacitance ideas and is proposed to arise from a correspondingly structured (e.g., not smooth) density of electronic states of the nanoparticle core, resulting from its small HOMO/LUMO gap and incipiently molecule-like behavior.     

Parabolic scaling of tree-shaped constructal network

We investigate the multi-scale structure of a tree network obtained by constructal theory and we propose a new geometrical framework to quantify deviations from scale invariance observed in many fields of physics and life sciences. We compare a constructally deduced fluid distribution network and one based on an assumed fractal algorithm. We show that: (i) the fractal network offers lower performance than the constructal object, and (ii) the constructal object exhibits a parabolic scaling explained in the context of the entropic skins geometry based on a scale diffusion equation in the scale space. Constructal optimization is equivalent to an equipartition of scale entropy production over scale space in the context of entropic skins theory. The association of constructal theory with entropic skins theory promises a deterministic theory to explain and build optimal arborescent structures.     

Combinatoric enumeration of two-dimensional proper arrays

An n×mproper array is a two-dimensional rectangular array composed of directed cubes that obey certain constraints. Because of these constraints, the n×m proper arrays may be classified via a schema in which each n×m proper array is associated with a particular n×1 column. For a fixed n, the goal is to enumerate, modulo symmetry, all possible edge configurations associated with n×m proper arrays. By varying n, one constructs four combinatoric sequences, each of which enumerates a particular class of edge configurations. Convolution arguments and resultant calculations associate these sequences with cubic equations. These cubic equations allow one to predict M_n, the number of edge configurations, modulo symmetry, associated with n×m proper arrays.     

A theoretical study of the barbier reaction

Semiempirical MO calculations are shown to provide a more detailed picture of the radical ion mechanism of the Barbier reaction in the general case. Calculated electron affinities give a clue for its extension to other cases.