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Unprecedented Noncanonical Features of the Nonlinear Nonribosomal Peptide Synthetase Assembly Line for WS9326A Biosynthesis

Systematic manipulation of the nonribosomal peptide synthetase (NRPS) domains in combination with elucidation of the interactions between the unique domains and structure revealed several hitherto unprecedented nonlinear NRPS assembly processes during the biosynthesis of cyclodepsipeptide WS9326A. Abstract Systematic inactivation of nonribosomal...

The Desensitized Channelrhodopsin‐2 Photointermediate Contains 13 ‐cis, 15 ‐syn Retinal Schiff Base

Channelrhodopsin-2, a light driven cation channel with a retinal chromophore, undergoes a cyclic photoreaction with several photointermediates. Here, we analyze the chromophore configuration of the intermediates, which can be cryo-trapped, in detail by DNP-enhanced solid-state NMR spectroscopy and reveal that the desensitized state is in a 13-cis,15-syn...

Healable and Rearrangeable Networks of Liquid Crystal Elastomers Enabled by Diselenide Bonds

A novel exchangeable diselenide chain extender is incorporated into an LCE system, bringing about the reprogrammability and the healability under visible-light irradiation or upon thermal treatment. These properties enable the utilization of a self-welding strategy to fabricate the complex LCE-based soft actuators without using any auxiliary reagent...

A Fully Coplanar Donor–Acceptor Polymeric Semiconductor with Promoted Charge Separation Kinetics for Photochemistry

Two polyarylether-based polymers with single/double linking patterns were investigated to establish the effect of the linking patterns on the charge generation and separation process in D–A conjugated polymer photocatalysts, thus achieving remarkable photocatalytic HER and HPER performances. Abstract Charge generation and separation are regarded...

Synthesis of Cyclic Anhydrides via Ligand‐Enabled C–H Carbonylation of Simple Aliphatic Acids

PdII-catalyzed β- or γ-C(sp3)–H carbonylation of free carboxylic acids, a new method for the synthesis of a wide range of cyclic anhydrides, is reported. Decarboxylative functionalization of the installed carboxyl group provides access to diverse β-functionalized aliphatic acids. The enantioselective C–H carbonylation of cyclopropanecarboxylic acids...

Water Oxidation under Modal Ultrastrong Coupling Conditions Using Au/Ag Alloy Nanoparticles and Fabry‐Pérot Nanocavities

We developed a photoanode consisting of Au-Ag alloy nanoparticles (NPs), a TiO 2 thin film and a Au film (AATA) under modal strong coupling conditions with a large splitting energy of 520 meV, which can be categorized into the "ultrastrong coupling regime". We fabricated a photoanode under ultrastrong coupling conditions to verify the relationship...

Na9Bi5Os3O24: A Diamagnetic Oxide Featuring a Pronouncedly Jahn–Teller‐Compressed Octahedral Coordination of Osmium(VI)

A Jahn–Teller-compressed OsO6 octahedron resulting in an unprecedented large splitting of the t 2g levels and a diamagnetic ground state has been observed. Abstract The Jahn–Teller (JT) theorem constitutes one of the most fundamental concepts in chemistry. In transition-element chemistry, the 3d4 and 3d9 configurations in octahedral complexes...

Discovery of a Low Thermal Conductivity Oxide Guided by Probe Structure Prediction and Machine Learning

Ba10Y6Ti4O27 has a complex aperiodic structure with the lowest thermal conductivity of any first-transition-series oxide. It is metastable, which makes it challenging to identify. Experimental exploration was focused sufficiently by structure prediction and property-targeted machine learning to enable the isolation of this material (see picture), whose...

Transition Metal Catalyst‐Free, Base‐Promoted 1,2‐Additions of Polyfluorophenylboronates to Aldehydes and Ketones

Herein we report a transition metal-free procedure for the base-promoted 1,2-addition of polyfluorophenylboronates to aldehydes and ketones to generate organofluorine-containing alcohols in yields up to 93 %. Abstract A novel protocol for the transition metal-free 1,2-addition of polyfluoroaryl boronate esters to aldehydes and ketones is reported,...

Photoelectron Circular Dichroism in the Photodetachment of Amino Acid Anions

The chirality of chemical compounds is of undisputed importance in science and technology. In particular with respect to pharmacological application most molecules of interest cannot be accessed by the powerful techniques developed in recent years for gas phase analytes. Here, we demonstrate that the combination of electrospray ionization (ESI) with...

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