Precise Synthesis and Thin Film Self-Assembly of PLLA-b-PS Bottlebrush Block Copolymers

The ability of bottlebrush block copolymers (BBCPs) to self-assemble into ordered large periodic structures could greatly expand the scope of photonic and membrane technologies. In this paper, we describe a two-step synthesis of poly(l-lactide)-b-polystyrene (PLLA-b-PS) BBCPs and their rapid thin-film self-assembly. PLLA chains were grown from exo-5-norbornene-2-methanol via ring-opening polymerization (ROP) of l-lactide to produce norbornene-terminated PLLA. Norbonene-terminated PS was prepared using anionic polymerization followed by a termination reaction with exo-5-norbornene-2-carbonyl chloride. PLLA-b-PS BBCPs were prepared from these two norbornenyl macromonomers by a one-pot sequential ring opening metathesis polymerization (ROMP). PLLA-b-PS BBCPs thin-films exhibited cylindrical and lamellar morphologies depending on the relative block volume fractions, with domain sizes of 46–58 nm and periodicities of 70–102 nm. Additionally, nanoporous templates were produced by the selective etching of PLLA blocks from ordered structures. The findings described in this work provide further insight into the controlled synthesis of BBCPs leading to various possible morphologies for applications requiring large periodicities. Moreover, the rapid thin film patterning strategy demonstrated (>5 min) highlights the advantages of using PLLA-b-PS BBCP materials beyond their linear BCP analogues in terms of both dimensions achievable and reduced processing time.     

μ-η6,η6-Arene-bridged diuranium hexakisketimide complexes isolable in two states of charge

Diuranium μ-η(6),η(6)-arene complexes supported by ketimide ligands were synthesized and characterized. Disodium or dipotassium salts of the formula M(2)(μ-η(6),η(6)-arene)[U(NC(t)BuMes)(3)](2) (M = Na or K, Mes = 2,4,6-C(6)H(2)Me(3)) and monopotassium salts of the formula K(μ-η(6),η(6)-arene)[U(NC(t)BuMes)(3)](2) (arene = naphthalene, biphenyl, trans-stilbene, or p-terphenyl) were both observed. Two different salts of the monoanionic, toluene-bridged complexes are also described. Density functional theory calculations have been employed to illuminate the electronic structure of the μ-η(6),η(6)-arene diuranium complexes and to facilitate the comparison with related transition-metal systems, in particular (μ-η(6),η(6)-C(6)H(6))[VCp](2). It was found that the μ-η(6),η(6)-arene diuranium complexes were isolobal with (μ-η(6),η(6)-C(6)H(6))[VCp](2) and that the principal arene-binding interaction was a pair of δ bonds (total of 4e) involving both metals and the arene lowest unoccupied molecular orbital. Reactivity studies have been carried out with the mono- and dianionic μ-η(6),η(6)-arene diuranium complexes, revealing contrasting modes of redox chemistry as a function of the system's state of charge.     

Three‐dimensional wave impact on a rigid structure using smoothed particle hydrodynamics

Navier–Stokes computations of a wave–structure interaction are performed with the aim of assessing the potential of smoothed particle hydrodynamics to accurately estimate impact loading time history. A three‐dimensional dam‐break flow with a rectangular column located downstream is considered. The net force and impulse exerted on the column is monitored throughout the simulation with the results correlating well with existing experimental data. Initial and boundary conditions and numerical parameters are varied and their effect on the column load investigated. The column load is found to be most sensitive to the choice of boundary treatment. Copyright © 2011 John Wiley & Sons, Ltd.     

磁瓶式光电子能谱和速度成像光电子能谱对APS-(A=C14H10,蒽)的研究:电子结构,APS·的自旋轨道耦合和APS-的自旋偶极态

Gaseous dibenzo-7-phosphanorbornadiene P-sulfide anions APS^-(A=C₁₄H₁₀ or anthracene) were generated via electrospray ionization, and characterized by magnetic-bottle photoelectron spectroscopy, velocity-map imaging (VMI) photoelectron spectroscopy, and quantum chemical calculations. The electron affinity (EA) and spin-orbit (SO) splitting of the APS^· radical are determined from the photoelectron spectra and Franck-Condon factor simulations to be EA=(2.62±0.05) eV and SO splitting=(43±7) meV. VMI photoelectron images show strong and sharp peaks near the detachment threshold with an identical electron kinetic energy (eKE) of 17.9 meV at three different detachment wavelengths, which are therefore assigned to autodetachment from dipole-bound anion states. The B3LYP/6-31++G(d,p) calculations indicate APS^· has a dipole moment of 3.31 Debye, large enough to support a dipole-bound electron.