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Self-assembly in systems based on L-cysteine-silver-nitrate aqueous solution: multiscale computer simulation.

Maxim D Malyshev1, Svetlana D Khizhnyak1, Lubov V Zherenkova1

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Multiscale simulations reveal silver mercaptide (SM) clusters form core-shell structures in silver nitrate-L-cysteine solutions. These clusters self-assemble into supramonomers, driving aggregate formation and phase transitions with varying salt concentrations.

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Area of Science:

  • Supramolecular chemistry
  • Computational materials science
  • Physical chemistry

Background:

  • Aqueous solutions of silver nitrate and L-cysteine (CSS) exhibit complex self-assembly behavior.
  • Understanding the multiscale structure formation is crucial for controlling solution properties.

Purpose of the Study:

  • To investigate the multiscale structure formation in CSS using computational simulations.
  • To elucidate the role of silver mercaptide clusters and supramonomers in aggregate formation.
  • To model the influence of salt concentration on structural transitions.

Main Methods:

  • Fully atomistic simulations to identify cluster structure.
  • Quantum mechanics calculations for intermolecular interactions.
  • Mesoscopic simulations with a "sticky spheres" model for aggregate behavior.

Main Results:

  • Atomistic models revealed core-shell silver mercaptide (SM) clusters.
  • SM clusters act as supramonomers through surface functional group interactions.
  • Mesoscopic models successfully reproduced CSS structural transitions (dispersion, gel, precipitation) with salt concentration.

Conclusions:

  • The study provides a multiscale computational framework for understanding CSS self-assembly.
  • Silver mercaptide cluster formation and supramonomer interactions are key to CSS structural evolution.
  • The mesoscopic model accurately predicts experimentally observed phase behaviors based on salt concentration.