Use of N‐methyliminodiacetic acid boronate esters in suzuki‐miyaura cross‐coupling polymerizations of triarylamine and fluorene monomers

Polytriarylamine copolymers can be prepared by Suzuki‐Miyaura cross‐coupling reactions of bis N‐methyliminodiacetic acid (MIDA) boronate ester substituted arylamines with dibromo arenes. The roles of solvent composition, temperature, reaction time, and co‐monomer structure were examined and (co)polymers prepared containing 9, 9‐dioctylfluorene (F8), 4‐sec‐butyl or 4‐octylphenyl diphenyl amine (TFB), and N, N′‐bis(4‐octylphenyl)‐N, N′‐diphenyl phenylenediamine (PTB) units, using a Pd(OAc)₂/2‐dicyclohexylphosphino‐2′,6′‐dimethoxybiphenyl (SPhos) catalyst system. The performance of a di‐functionalized MIDA boronate ester monomer was compared with that of an equivalent pinacol boronate ester. Higher molar mass polymers were produced from reactions starting with a difunctionalized pinacol boronate ester monomer than the equivalent difunctionalized MIDA boronate ester monomer in biphase solvent mixtures (toluene/dioxane/water). Matrix‐assisted laser desorption/ionization mass spectroscopic analysis revealed that polymeric structures rich in residues associated with the starting MIDA monomer were present, suggesting that homo‐coupling of the boronate ester must be occurring to the detriment of cross‐coupling in the step‐growth polymerization. However, when comparable reactions of the two boronate monomers with a dibromo fluorene monomer were completed in a single phase solvent mixture (dioxane + water), high molar mass polymers with relatively narrow distribution ranges were obtained after only 4 h of reaction. © 2017 The Authors. Journal of Polymer Science Part A: Polymer Chemistry Published by Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2798–2806     

Single particle tracking as a method to resolve differences in highly colocalized proteins

Single particle tracking fluorescence microscopy was used to study two late endosomal proteins, Rab7 and LAMP1, that appear to be highly colocalized in static fluorescence microscopy images. Imaging these proteins simultaneously reveals that Rab7 and LAMP1 undergo periods of separation within the cell. Single particle tracking carried out during these periods of separation shows that Rab7-vesicles have greater velocities, but undergo less efficient transport than LAMP1-vesicles. This research demonstrates the use of single particle tracking as a tool to resolve functional differences in highly colocalized proteins in intact live cells.     

Platinum-catalysed allylic alkylation: reactivity, enantioselectivity, and regioselectivity

The use of platinum complexes as catalysts for allylic substitution has been studied. A variety of different complexes catalyse the reaction, and several substrates have been tested. In the alkylation of mono(alkyl)-substituted allylic acetates, regioselectivity is highly dependent on ligand choice. By using tricyclohexylphosphine as the ligand, almost complete formation of branched products is observed. The development of a highly enantioselective (ca. 80-90% ee) reaction that makes use of chiral diphenylphosphinooxazoline ligands (abbreviated as (S)-PN) is also described. The enantioselectivity is highly dependent on the ratio of ligand to platinum (when the ratio ligand/Pt is greater than 1:1, the ee drops off dramatically). This is in contrast to palladium and is interpreted in terms of differing coordination chemistry for the two metals ((S)-PN is hemilabile when complexed to platinum) and should be of significance to future systems that utilise heterobidentate ligands. The crystal structures of two isoelectronic platinum and palladium complexes [[(S)-PN]MCl2] are also described.     

A Conventional Surfactant Becomes CO2‐Responsive in the Presence of Switchable Water Additives

We have developed a new benign means of reversibly breaking emulsions and latexes by using “switchable water”, an aqueous solution of switchable ionic strength. The conventional surfactant sodium dodecyl sulfate (SDS) is not normally stimuli‐responsive when CO₂ is used as the stimulus but becomes CO₂‐responsive or “switchable” in the presence of a switchable water additive. In particular, changes in the air/water surface tension and oil/water interfacial tension can be triggered by addition and removal of CO₂. A switchable water additive, N,N‐dimethylethanolamine (DMEA), was found to be an effective and efficient additive for the reversible reduction of interfacial tension and can lower the tension of the dodecane/water interface in the presence of SDS surfactant to ultra‐low values at very low additive concentrations. Switchable water was successfully used to reversibly break an emulsion containing SDS as surfactant, and dodecane as organic liquid. Also, the addition of CO₂ and switchable water can result in aggregation of polystyrene (PS) latexes; the later removal of CO₂ neutralizes the DMEA and decreases the ionic strength allowing for the aggregated PS latex to be redispersed and recovered in its original state.     

Spatial disorder in a smectic A mesophase

Starting with the equations of motion for a stiff chain, a projection operator approach is utilized to develop diffusional equations for the dynamics of the end-to-end distance. The diffusion equation resulting has a spatial-dependent diffusion coefficient calculable from equilibrium properties of the chain, and a frequency-dependent part which requires dynamical information. The analysis is applied, in so far as the spatial dependence of D is determined, for three and four bond chains. A critique of this procedure is provided.     

Approximation and Equidistribution of Phase Shifts: Spherical Symmetry

Consider a semiclassical Hamiltonian $$H_{V, h} := h^{2} \Delta + V - E,$$ where h > 0 is a semiclassical parameter, Δ is the positive Laplacian on ${\mathbb{R}^{d}, V}$ is a smooth, compactly supported central potential function and E > 0 is an energy level. In this setting the scattering matrix S _h (E) is a unitary operator on ${L^2(\mathbb{S}^{d-1})}$ , hence with spectrum lying on the unit circle; moreover, the spectrum is discrete except at 1. We show under certain additional assumptions on the potential that the eigenvalues of S _h (E) can be divided into two classes: a finite number ${\sim c_d (R\sqrt{E}/h)^{d-1}}$ , as ${h \to 0}$ , where B(0, R) is the convex hull of the support of the potential, that equidistribute around the unit circle, and the remainder that are all very close to 1. Semiclassically, these are related to the rays that meet the support of, and hence are scattered by, the potential, and those that do not meet the support of the potential, respectively. A similar property is shown for the obstacle problem in the case that the obstacle is the ball of radius R.     

Towards antihydrogen trapping and spectroscopy at ALPHA

Spectroscopy of antihydrogen has the potential to yield high-precision tests of the CPT theorem and shed light on the matter-antimatter imbalance in the Universe. The ALPHA antihydrogen trap at CERN??s Antiproton Decelerator aims to prepare a sample of antihydrogen atoms confined in an octupole-based Ioffe trap and to measure the frequency of several atomic transitions. We describe our techniques to directly measure the antiproton temperature and a new technique to cool them to below 10 K. We also show how our unique position-sensitive annihilation detector provides us with a highly sensitive method of identifying antiproton annihilations and effectively rejecting the cosmic-ray background.