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Biochemical specificity is critical in enzyme function, evolution, and engineering. Here we employ an established kinetic model to dissect the effects of reactant geometry and diffusion on product formation speed and accuracy in the presence of cognate (correct) and near-cognate (incorrect) substrates. Using this steady-state model for spherical geometries, we find that, for distinct kinetic regimes, the speed and accuracy of the reactions are optimized on different regions of the geometric landscape. From this model we deduce that accuracy can be strongly dependent on reactant geometric properties even for chemically limited reactions. Notably, substrates with a specific geometry and reactivity can be discriminated by the enzyme with higher efficacy than others through purely diffusive effects. For similar cognate and near-cognate substrate geometries (as is the case for polymerases or the ribosome), we observe that speed and accuracy are maximized in opposing regions of the geometric landscape. We also show that, in relevant environments, diffusive effects on accuracy can be substantial even far from extreme kinetic conditions. Finally, we find how reactant chemical discrimination and diffusion can be related to simultaneously optimize steady-state flux and accuracy. These results highlight how diffusion and geometry can be employed to enhance reaction speed and discrimination, and similarly how they impose fundamental restraints on these quantities.
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This content will become publicly available on May 15, 2026
Steady-State Synthesis of Colloidal Metal Nanocrystals
Despite remarkable progress, colloidal synthesis of metal nanocrystal is still far away from reaching the goal for robust, reproducible, and scalable production. Even with the adoption of seed-mediated growth, the synthesis can still be complicated by issues such as self-nucleation, galvanic replacement, stochastic symmetry reduction, and unwanted compositional variation. All these issues can be addressed by switching to steady-state synthesis characterized by a slow, constant, and tightly controlled reduction rate. Steady-state synthesis can be achieved by adding one reactant dropwise while using the other reactant in large excess, but this method is not suitable for scale-up production in a continuous flow reactor. There is a pressing need to develop alternative methods capable of establishing the steady-state kinetics characteristic of dropwise addition while introducing both reactants by one-shot injection. In this Perspective, we discuss a number of methods that allow for both one-shot injection and steady-state synthesis.
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- PAR ID:
- 10627938
- Publisher / Repository:
- Scilight
- Date Published:
- Journal Name:
- Materials and Interfaces
- ISSN:
- 2982-2394
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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