Composition Operators and Endomorphisms

If b is an inner function, then composition with b induces an endomorphism, β, of L^￥(\mathbbT){L^\infty({\mathbb{T}})} that leaves H^￥(\mathbbT){H^\infty({\mathbb{T}})} invariant. We investigate the structure of the endomorphisms of B(L²(\mathbbT)){B(L^2({\mathbb{T}}))} and B(H²(\mathbbT)){B(H^2({\mathbb{T}}))} that implement β through the representations of L^￥(\mathbbT){L^\infty({\mathbb{T}})} and H^￥(\mathbbT){H^\infty({\mathbb{T}})} in terms of multiplication operators on L²(\mathbbT){L^2({\mathbb{T}})} and H²(\mathbbT){H^2({\mathbb{T}})} . Our analysis, which is based on work of Rochberg and McDonald, will wind its way through the theory of composition operators on spaces of analytic functions to recent work on Cuntz families of isometries and Hilbert C*-modules.     

A General Approach to Intermolecular Olefin Hydroacylation through Light-Induced HAT Initiation: An Efficient Synthesis of Long-Chain Aliphatic Ketones and Functionalized Fatty Acids

Herein, an operationally simple, environmentally benign and effective method for intermolecular radical hydroacylation of unactivated substrates by employing photo-induced hydrogen atom transfer (HAT) initiation is described. The use of commercially available and inexpensive photoinitiators (Ph₂CO and NHPI) makes the process attractive. The olefin hydroacylation protocol applies to a wide array of substrates bearing numerous functional groups and many complex structural units. The reaction proves to be scalable (up to 5 g). Different functionalized fatty acids, petrochemicals and naturally occurring alkanes can be synthesized with this protocol. A radical chain mechanism is implicated in the process.     

Molecular QTAIM Topology Is Sensitive to Relativistic Corrections

The topology of the molecular electron density of benzene dithiol gold cluster complex Au₄−S−C₆H₄−S′−Au′₄ changed when relativistic corrections were made and the structure was close to a minimum of the Born–Oppenheimer energy surface. Specifically, new bond paths between hydrogen atoms on the benzene ring and gold atoms appeared, indicating that there is a favorable interaction between these atoms at the relativistic level. This is consistent with the observation that gold becomes a better electron acceptor when relativistic corrections are applied. In addition to relativistic effects, here, we establish the sensitivity of molecular topology to basis sets and convergence thresholds for geometry optimization.     

S‐Adenosyl Methionine Cofactor Modifications Enhance the Biocatalytic Repertoire of Small Molecule C‐Alkylation

A tandem enzymatic strategy to enhance the scope of C‐alkylation of small molecules via the in situ formation of S‐adenosyl methionine (SAM) cofactor analogues is described. A solvent‐exposed channel present in the SAM‐forming enzyme SalL tolerates 5′‐chloro‐5′‐deoxyadenosine (ClDA) analogues modified at the 2‐position of the adenine nucleobase. Coupling SalL‐catalyzed cofactor production with C‐(m)ethyl transfer to coumarin substrates catalyzed by the methyltransferase (MTase) NovO forms C‐(m)ethylated coumarins in superior yield and greater substrate scope relative to that obtained using cofactors lacking nucleobase modifications. Establishing the molecular determinants that influence C‐alkylation provides the basis to develop a late‐stage enzymatic platform for the preparation of high value small molecules.     

Influence of the pH Value on the Hydrothermal Degradation of Fructose

The hydrothermal treatment of sugars features a promising technology for the production of fine and platform chemicals from renewable resources. In this work the hydrothermal decomposition of fructose was studied in a buffered medium at a pH range between 2.2 and 8.0. It is demonstrated that at lower pH values mainly 5-hydroxymethylfurfural (HMF), levulinic acid and humin are generated, while lactic acid and acetic acid are produced at higher pH values. The work shows that the use of moderate acidic conditions may have advantages for the hydrothermal HMF production over the use of strongly acidic conditions, as especially the degradation into levulinic acid is suppressed. Besides, this study deals with a rather complex reaction network, hence limitations and need for adaption of the kinetic model are discussed.     

Some Aspects of Intra- and Inter-Molecular Reactions of Siliconium Ions in the Vapor Phase

Intramolecular rearrangement processes in the mass spectra of trimethylsilyl derivatives of hydroxy steroids are discussed in terms of the reaction of a siliconium center and a heteroatom. The reaction is shown to be stereospecific. The reactivity of siliconium cations also results in the occurrence of intermolecular reactions under electron impact ionization conditions. Tetramethylsilane is used as a precursor for the production of siliconium ions and examples of chemical ionization mass spectra employing this reagent are shown.     

Preparation,Crystal Structure and Properties of Spirophosphoranes Derived from Hydroxycarboxylic Acid Azides

Abstract

Spirophosphoranes are produced by reaction of 2–phenyl–1,3,2–dioxaphospholane with both 2- and 3–hydroxycarboxylic acid azides, whereas 1–phenyl–phospholane yields spirophosphoranes only upon reaction with the former. The structures of two spirophosphoranes have been determined by X-ray analysis.     

Controlling domain orientation of liquid crystalline block copolymer in thin films through tuning mesogenic chemical structures

Controlling the macroscopic orientation of nanoscale periodic structures of amphiphilic liquid crystalline block copolymers (LC BCPs) is important to a variety of technical applications (e.g., lithium conducting polymer electrolytes). To study LC BCP domain orientation, a series of LC BCPs containing a poly(ethylene oxide) (PEO) block as a conventional hydrophilic coil block and LC blocks containing azobenzene mesogens is designed and synthesized. LC ordering in thin films of the BCP leads to the formation of highly ordered, microphase‐separated nanostructures, with hexagonally arranged PEO cylinders. Substitution on the tail of the azobenzene mesogen is shown to control the orientation of the PEO cylinders. When the substitution on the mesogenic tails is an alkyl chain, the PEO cylinders have a perpendicular orientation to the substrate surface, provided the thin film is above a critical thickness value. In contrast, when the substitution on the mesogenic tails has an ether group the PEO cylinders assemble parallel to the substrate surface regardless of the film thickness value. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 532–541