Revealing the Unique Role of Water in the Formation of Benzothiazoles: an Experimental and Computational Study.

We present here a joint experimental and computational study on the formation of benzothiazoles. Our investigation reveals a green protocol for accessing benzothiazoles from acyl chlorides using either water alongside a reducing agent as the reaction medium or in combination with stoichiometric amounts of a weak acid, instead of the harsh conditions and catalysts previously reported. Specifically, we show that a protic solvent, particularly water, enables the formation of 2-substituted benzothiazoles from N-acyl 1,2-aminothiophenols already at room temperature, without the need for strong acids or metal catalysts. DFT Molecular Dynamics simulations coupled with advanced enhanced sampling techniques provide a clear understanding of the catalytic role of water. We demonstrate how bulk water - due to its extended network of hydrogen bonds and an efficient Grotthuss mechanism - provides a reaction path that strongly reduces the reaction barriers compared to aprotic environments, namely more than 80 kJ/mol for the first reaction step and 250 kJ/mol for the second. Finally, we discuss the influence of different aliphatic and aromatic substituents with varying electronic properties on chemical reactivity. Besides providing in-depth mechanistic insights, we believe that our findings pave the way for a greener route toward an important class of bioactive molecules.

Microfluidic Design of Streamlined Alginate Hydrogel Micromotors with Run and Tumble Motion Patterns.

Autonomous micromotors demonstrate remarkable advancements in biomedical applications. A noteworthy example is streamlined motors, which display enhanced movement efficiency with low fluid-resistance. However, existing streamlined motors, primarily constructed from inorganic materials, present challenges due to their complex fabrication procedures and lack of a soft interface for interaction with biological systems. Herein, a novel design of biodegradable streamlined alginate hydrogel micromotors with a teardrop shape by microfluidics is introduced. The platform enables the high-throughput fabrication of monodisperse micromotors with varied dimensions. By incorporating Pt-coated Fe3 O4 nanoparticles, micromotors are equipped with dual capabilities of catalytic propulsion and accurate magnetic guidance. Through precisely tuning the localization regions of catalysts within the micromotors, the streamlined hydrogel micromotors not only exhibit enhanced propelling efficiency, but also accomplish distinct motion patterns of run and tumble. The design provides insights for developing advanced micromotors capable of executing intricate tasks across diverse application scenarios.