The Precise Synthesis of Ultradense Bottlebrush Polymers Unearths Unique Trends in Lyotropic Ordering.

Biomacromolecular networks with multiscale fibrillar structures are characterized by exceptional mechanical properties, making them attractive architectures for synthetic materials. However, there is a dearth of synthetic polymeric building blocks capable of forming similarly structured networks. Bottlebrush polymers (BBPs) are anisotropic graft polymers with the potential to mimic and replace biomacromolecules such as tropocollagen for the fabrication of synthetic fibrillar networks; however, a longstanding limitation of BBPs has been the lack of rigidity necessary to access the lyotropic ordering that underpins the formation of collagenous networks.

Ion-Specific Interactions Engender Dynamic and Tailorable Properties in Biomimetic Cationic Polyelectrolytes.

Biomaterials such as spider silk and mussel byssi are fabricated by the dynamic manipulation of intra- and intermolecular biopolymer interactions. Organisms modulate solution parameters, such as pH and ion co-solute concentration, to effect these processes. These biofabrication schemes provide a conceptual framework to develop new dynamic and responsive abiotic soft material systems.

Correction: Reductive annulations of arylidene malonates with unsaturated electrophiles using photoredox/Lewis acid cooperative catalysis.

[This corrects the article DOI: 10.1039/C9SC00302A.].

Dynamic Coloration of Complex Emulsions by Localization of Gold Rings Near the Triphase Junction.

Multiphase microscale emulsions are a material platform that can be tuned and dynamically configured by a variety of chemical and physical phenomena, rendering them inexpensive and broadly programmable optical transducers. Interface engineering underpins many of these sensing schemes but typically focuses on manipulating a single interface, while engineering of the multiphase junctions of complex emulsions remains underexplored. Herein, multiphilic triblock copolymer surfactants are synthesized and assembled at the triphase junction of a dynamically reconfigurable biphasic emulsion.

High-throughput photocapture approach for reaction discovery.

Modern organic reaction discovery and development relies on the rapid assessment of large arrays of hypothesis-driven experiments. The time-intensive nature of reaction analysis presents the greatest practical barrier for the execution of this iterative process that underpins the development of new bioactive agents. Toward addressing this critical bottleneck, we report herein a high-throughput analysis (HTA) method of reaction mixtures by photocapture on a 384-spot diazirine-terminated self-assembled monolayer, and self-assembled monolayers for matrix-assisted laser desorption/ionization mass spectrometry (SAMDI-MS) analysis.

Chemiresistive Sensor Array and Machine Learning Classification of Food.

Successful identification of complex odors by sensor arrays remains a challenging problem. Herein, we report robust, category-specific multiclass-time series classification using an array of 20 carbon nanotube-based chemical sensors. We differentiate between samples of cheese, liquor, and edible oil based on their odor.

Reductive annulations of arylidene malonates with unsaturated electrophiles using photoredox/Lewis acid cooperative catalysis.

A cooperative Lewis acid/photocatalytic reduction of salicylaldehyde-derived arylidene malonates provides access to a versatile, stabilized radical anion enolate. Using these unusual umpolung operators, we have developed a novel route to access densely functionalized carbo- and heterocycles through a radical annulation addition pathway.

Intermolecular Reductive Couplings of Arylidene Malonates via Lewis Acid/Photoredox Cooperative Catalysis.

A cooperative Lewis acid/photocatalytic reduction of arylidene malonates yields a versatile radical anion species. This intermediate preferentially undergoes intermolecular radical-radical coupling reactions, and not the conjugate addition-dimerization reactivity typically observed in the single-electron reduction of conjugate acceptors. Reported here is the development of this open-shell species in intermolecular radical-radical cross couplings, radical dimerizations, and transfer hydrogenations.

Pyranone natural products as inspirations for catalytic reaction discovery and development.

Natural products continue to provide a wealth of opportunities in the areas of chemical and therapeutic development. These structures are effective measuring sticks for the current state of chemical synthesis as a field and constantly inspire new approaches and strategies. Tetrahydropryans and tetrahydropyran-4-ones are found in numerous bioactive marine natural products and medicinal compounds.

A biomimetic strategy to access the silybins: total synthesis of (-)-isosilybin A.

We report the first asymmetric, total synthesis of (-)-isosilybin A. A late-stage catalytic biomimetic cyclization of a highly functionalized chalcone is employed to form the characteristic benzopyranone ring. A robust and flexible approach to this chalcone provides an entry to the preparation of the entire isomeric family of silybin natural products.