Zwitterionic Diphenylphosphinyl Amidate as a Powerful Photoinduced Hydrogen-Atom-Transfer Catalyst for C-H Alkylation of Simple Alkanes.

The chemical and physical properties of amides change substantially when the electron-withdrawing groups attached to the nitrogen are varied. Herein, we report the superior performance of N-diphenylphosphinyl 1,2,3-triazolium amidate as a photoinduced hydrogen-atom transfer catalyst compared to its N-benzoyl analog. A binary catalyst system of the phosphinyl amidate and an Ir-based photocatalyst enables the alkylation of unbiased C-H bonds.

Hydrogen-Atom Transfer Catalysis for C-H Alkylation of Benzylic Fluorides.

A photoinduced catalytic C(sp3)-H alkylation of benzylic fluorides is developed. The use of zwitterionic 1,2,3-triazolium amidate as a hydrogen-atom transfer catalyst is uniquely effective for promoting this transformation. The combination of C-H alkylation with subsequent displacement of the C-F bond enables 1,1-difunctionalization of benzylic fluorides, providing rapid access to an array of functionalized molecular entities.

DNA-assisted swarm control in a biomolecular motor system.

In nature, swarming behavior has evolved repeatedly among motile organisms because it confers a variety of beneficial emergent properties. These include improved information gathering, protection from predators, and resource utilization. Some organisms, e.g., locusts, switch between solitary and swarm behavior in response to external stimuli. Aspects of swarming behavior have been demonstrated for motile supramolecular systems composed of biomolecular motors and cytoskeletal filaments, where cross-linkers induce large scale organization. The capabilities of such supramolecular systems may be further extended if the swarming behavior can be programmed and controlled. Here, we demonstrate that the swarming of DNA-functionalized microtubules (MTs) propelled by surface-adhered kinesin motors can be programmed and reversibly regulated by DNA signals. Emergent swarm behavior, such as translational and circular motion, can be selected by tuning the MT stiffness. Photoresponsive DNA containing azobenzene groups enables switching between solitary and swarm behavior in response to stimulation with visible or ultraviolet light.

Localized lesions of ventral striatum, but not arcopallium, enhanced impulsiveness in choices based on anticipated spatial proximity of food rewards in domestic chicks.

The effects of bilateral chemical lesions of the ventral striatum (nucleus accumbens and the surrounding areas in the medial striatum) and arcopallium (major descending area of the avian telencephalon) were examined in 1-2-weeks old domestic chicks. Using a Y-maze, we analyzed the lesion effects on the choices that subject chicks made in two tasks with identical economical consequences, i.e., a small-and-close food reward vs. a large-and-distant food reward. In task 1, red, yellow, and green beads were associated with a feeder placed at various distances from the chicks; chicks thus anticipated the spatial proximity of food by the bead's color, whereas the quantity of the food was fixed. In task 2, red and yellow flags on the feeders were associated with various amount of food; the chicks thus anticipated the quantity of food by the flag's color, whereas the proximity of the reward could be directly visually determined. In task 1, bilateral lesions of the ventral striatum (but not the arcopallium) enhanced the impulsiveness of the chicks' choices, suggesting that choices based on the anticipated proximity were selectively changed. In task 2, similar lesions of the ventral striatum did not change choices. In both experiments, motor functions of the chicks remained unchanged, suggesting that the lesions did not affect the foraging efficiency, i.e., objective values of food. Neural correlates of anticipated food rewards in the ventral striatum (but not those in the arcopallium) could allow chicks to invest appropriate amount of work-cost in approaching distant food resources.