Ben Roberts

@benjaminoacid.bsky.social

Chemistry, molecular machines and other nonequilibrium stuff. Postdoc in the Prins group at UniPD. Overly enthusiastic about tea. https://orcid.org/0000-0003-2820-8359

Researchers at the University of Ulm have described the first autonomous walking small-molecule machine: a simple phosphate group. The walker travels along a hydroxy-paved molecular track using an alternating series of cyclization and ring-opening reactions. #chemsky 🧪

One small step for phosphate, one giant leap for molecular machine-kind

The first chemically fueled small-molecule walker dances around a sugar molecule without falling off

cen.acs.org

...“Concerning Demons... Is the production of an inequality of temperature their only occupation? No... demons can produce a difference in pressure by allowing all particles going in one direction while stopping all those going the other way. This reduces the demon to a valve” 😈 tinyurl.com/3ja25xfz

📢 Hiring a postdoc! Join my group on an NIH-funded project developing hydrazone-based photoswitchable fluorophores for super-resolution microscopy. Looking for expertise in organic synthesis, photochemistry, spectroscopy, systems/supramolecular chemistry, and/or chemical biology. #chemjobs #chemsky

Chemistry involves such large and small numbers that it’s often hard to take in just how fast some processes occur. Dethreading a ring off the open end of a chain when there are no binding interactions present, or passing the end of one strand past another, are incredibly fast processes...

Can you work out how fast a molecular motor rotates from in situ measurments? Turns out that yes, you can, as we show today in @jacs.acspublications.org pubs.acs.org/doi/10.1021/... @profdaveleigh.bsky.social @stefanborsley.bsky.social

In Situ Quantification of Directional Rotation by a Catalysis-Driven Azaindole-N-Oxide–Phenoic Acid Molecular Motor

We report the in situ quantification of directional rotation of a new type of catalysis-driven rotary motor featuring a phenyl carboxylic acid rotor attached to a 7-azaindole-N-oxide stator through a biaryl C–N bond. Continuous directional rotation of the rotor about the stator is driven by the achiral motor’s rotary catalysis of carbodiimide hydration in the presence of a chiral pyrrolidinylpyridine-N-oxide. The catalytic cycle features an intermediate O-acyl-azaindole-N-oxide ester tether formed between the carboxylic acid of the rotor and the N-oxide of the stator. Face-selective cleavage of the tether by the chiral pyrrolidinylpyridine-N-oxide additive generates relatively long-lived diastereomeric pyridine-N-oxide esters of the phenyl carboxylic acid. These are hydrolyzed during the catalytic cycle to reform the carboxylic acid resting state of the motor, completing net directional 360° rotation. In contrast to previous catalysis-driven motor-molecules, the motor’s directionality could be determined directly from the transient concentrations of the diastereomeric intermediates formed during rotary catalysis. This avoids reliance on restricted rotation models to assess motor directionality and provides direct access to other key performance indicators such as motor speed and catalytic, coupling and fuel efficiency. The in situ-determined directionality of the motor was found to be in excellent agreement with the directionality determined from a restricted rotation model, supporting both the efficacy of the new approach and the validity of using appropriately designed restricted rotation models. The results establish a straightforward method for the in situ quantification of various aspects of motor behavior, aiding the design and optimization of artificial molecular motors.

pubs.acs.org