Highly oriented and ordered microstructures in block copolymer films

Block copolymer (BCP) films with long-range lateral ordering and orientation are crucial for many applications. Here, we report a simple, versatile strategy based on a solution casting procedure, to produce millimeter thick film of BCPs with highly oriented nanostructures. Transmission electron microscope (TEM), small angle X-ray scattering (SAXS), and Hansen solubility parameters were used to study the morphology and interactions of the system. A variety of BCP-solvent pairs were investigated. Factors including set-up geometry, BCP characteristics, solvent evaporation, surface tension, and interactions, such as solvent-BCP, solvent-substrate, and BCP-substrate were examined. A mechanism is proposed to describe the observed long-range lateral ordering and orientation in films up to 1 mm in thickness. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 1369–1375     

ELECTRON-TRANSFER PROCESSES. PART 40. REACTION OF ALKYL RADICALS WITH DIPHENYLPHOSPHIDE ANION

Abstract

The anion Ph₂P^? (K⁺, 18-crown-6) reacts with t-BuHgCl in HMPA to form Ph₂PCMe₃ by a free radical chain mechanism. In Me₂SO, Ph₂P(O)CMe₃ is produced. Reaction of Ph₂P^? with PhCOCH₂HgCl yields the oxidative dimerization product isolable from HMPA but readily converted to Ph₂P(O)P(O)Ph₂ in Me₂SO.     

The structure of higher degree symmetry classes of tensors II

Various results bearing on the construction of bases for symmetry classes of tensors are discussed. Applications are given to the production of explicit homogeneous polynomial representations of the full linear group.     

Reduction Principle and Asymptotic Phase for Center Manifolds of Parabolic Systems with Nonlinear Boundary Conditions

We prove the reduction principle and study other attractivity properties of the center and center-unstable manifolds in the vicinity of a steady-state solution for quasilinear systems of parabolic partial differential equations with fully nonlinear boundary conditions on bounded or exterior domains.     

Stable,High‐Molecular‐Weight Poly(phthalaldehyde)

Low ceiling temperature, thermodynamically unstable polymers have been troublesome to synthesize and keep stable during storage. In this study, stable poly(phthalaldehyde) has been synthesized with BF₃‐OEt₂ catalyst. The role of BF₃ in the polymerization is described. The interaction of BF₃ with the monomer is described and used to maximize the yield and molecular weight of poly(phthalaldehyde). Various Lewis acids were used to investigate the effect of catalyst acidity on poly(phthalaldehyde) chain growth. In situ nuclear magnetic resonance was used to identify possible interactions formed between BF₃ and phthalaldehyde monomer and polymer. The molecular weight of the polymer tracks with polymerization yield. The ambient temperature stability of poly(phthalaldehyde) was investigated and the storage life of the polymer has been improved. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 55, 1166–1172     

Hybridorubrins A–D: Azaphilone Heterodimers from Stromata of Hypoxylon fragiforme and Insights into the Biosynthetic Machinery for Azaphilone Diversification

The diversity of azaphilones in stromatal extracts of the fungus Hypoxylon fragiforme was investigated and linked to their biosynthetic machineries by using bioinformatics. Nineteen azaphilone-type compounds were isolated and characterized by NMR spectroscopy and mass spectrometry, and their absolute stereoconfigurations were assigned by using Mosher ester analysis and electronic circular dichroism spectroscopy. Four unprecedented bis-azaphilones, named hybridorubrins A–D, were elucidated, in addition to new fragirubrins F and G and various known mitorubrin derivatives. Only the hybridorubrins, which are composed of mitorubrin and fragirubrin moieties, exhibited strong inhibition of Staphylococcus aureus biofilm formation. Analysis of the genome of H. fragiforme revealed the presence of two separate biosynthetic gene clusters (BGCs) hfaza1 and hfaza2 responsible for azaphilone formation. While the hfaza1 BGC likely encodes the assembly of the backbone and addition of fatty acid moieties to yield the (R)-configured series of fragirubrins, the hfaza2 BGC contains the necessary genes to synthesise the widely distributed (S)-mitorubrins. This study is the first example of two distant cross-acting fungal BGCs collaborating to produce two families of azaphilones and bis-azaphilones derived therefrom.