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Surface plasmon resonance (SPR) chips are widely used to measure associationand dissociation rates for the binding kinetics between two species ofchemicals, e.g., cell receptors and ligands. It is commonly assumed thatligands are spatially well mixed in the SPR region, and hence a mean-field rateequation description is appropriate. This approximation however ignores thespatial fluctuations as well as temporal correlations induced by multiple localrebinding events, which become prominent for slow diffusion rates and highbinding affinities. We report detailed Monte Carlo simulations of ligandbinding kinetics in an SPR cell subject to laminar flow. We extract the bindingand dissociation rates by means of the techniques frequently employed inexperimental analysis that are motivated by the mean-field approximation. Wefind major discrepancies in a wide parameter regime between the thus extractedrates and the known input simulation values. These results underscore thecrucial quantitative importance of spatio-temporal correlations in binaryreaction kinetics in SPR cell geometries, and demonstrate the failure of amean-field analysis of SPR cells in the regime of high Damk\"ohler number Da >0.1, where the spatio-temporal correlations due to diffusive transport andligand-receptor rebinding events dominate the dynamics of SPR systems.

Ligand-receptor binding kinetics in surface plasmon resonance cells: A Monte Carlo analysis