Exact concentration regions for stimulus-switched competitive binding under finite depletion.
- 1Independent Researcher Seoul Republic of Korea [email protected].
Abstract
Transferring binary binding constants into competitive mixtures is a common but rarely validated step in stimulus-programmed molecular recognition. A pH-programmed Co₈L₁₂ coordination cage reported by Cullen et al., Chem. Sci., 2015, 6, 4025-4028 supplies a parameter-free test because its reported C/B composition at pH 7.5 requires K eff B(7.5) < 6.39 M⁻¹, yet the entire rectangle formed from the quoted marginal affinity ranges lies above this bound, with the most favourable point still giving 8.78 M⁻¹. This study develops a method that accounts for finite depletion, which separates concentration-window limitations from parameter-transfer failure. For two guests with one total fixed, monotonicity converts independent fidelity and occupancy targets into one-sided thresholds whose intersection is the complete admissible interval. A pairwise endpoint bound extends the consistency test to mixtures with additional same-site competitors, and a free-host-parametrized boundary construction maps the admissible region when two totals vary independently. For the Co₈L₁₂ cage reported by Cullen et al., Chem. Sci., 2015, 6, 4025-4028, a reference model neglecting depletion predicts a controlled-free-concentration reference of 95.95%, while the exact finite-depletion maximin is restricted to 94.36%. Conversely, a pH-responsive naphthotube operating with a wider selectivity margin retains a broad 95% target window and requires only a minor 0.22 percentage-point adjustment for depletion effects. The method therefore identifies when finite depletion changes a design decision and when transferred binary constants are inconsistent with competitive-mixture observations.
Versions
Related
- Nanodiamond-Enabled Passively Q-Switched Solid-State Laser Operating at 2 μm
- Photo‐Switched Catalytic Amyloids
- Chiral Anthranyl Bis-sulfoxides with Modular Chiroptical Properties Controlled by an Ionic Stimulus
- Research on Reversible Wetting Regulation and Interfacial Adaptive Behavior of Multi-Stimulus Responsive Nanoparticles
- Stimulus-responsive molecularly imprinted polymers for bisphenol A and dibutyl phthalate: Analytical trends, challenges, and future perspectives
BibTeX
@article{seo2026exact,
title = {{Exact concentration regions for stimulus-switched competitive binding under finite depletion.}},
author = {Hyun Seo},
journal = {RSC advances},
year = {2026},
month = oct,
doi = {10.1039/d6ra06172a},
url = {https://europepmc.org/article/MED/42847052},
note = {CC BY},
}
RIS
TY - JOUR
TI - Exact concentration regions for stimulus-switched competitive binding under finite depletion.
AU - Hyun Seo
PY - 2026
DA - 2026/10/07
JO - RSC advances
DO - 10.1039/d6ra06172a
UR - https://europepmc.org/article/MED/42847052
AB - Transferring binary binding constants into competitive mixtures is a common but rarely validated step in stimulus-programmed molecular recognition. A pH-programmed Co₈L₁₂ coordination cage reported by Cullen et al., Chem. Sci., 2015, 6, 4025-4028 supplies a parameter-free test because its reported C/B composition at pH 7.5 requires K eff B(7.5) < 6.39 M⁻¹, yet the entire rectangle formed from the quoted marginal affinity ranges lies above this bound, with the most favourable point still giving 8.78 M⁻¹. This study develops a method that accounts for finite depletion, which separates concentration-window limitations from parameter-transfer failure. For two guests with one total fixed, monotonicity converts independent fidelity and occupancy targets into one-sided thresholds whose intersection is the complete admissible interval. A pairwise endpoint bound extends the consistency test to mixtures with additional same-site competitors, and a free-host-parametrized boundary construction maps the admissible region when two totals vary independently. For the Co₈L₁₂ cage reported by Cullen et al., Chem. Sci., 2015, 6, 4025-4028, a reference model neglecting depletion predicts a controlled-free-concentration reference of 95.95%, while the exact finite-depletion maximin is restricted to 94.36%. Conversely, a pH-responsive naphthotube operating with a wider selectivity margin retains a broad 95% target window and requires only a minor 0.22 percentage-point adjustment for depletion effects. The method therefore identifies when finite depletion changes a design decision and when transferred binary constants are inconsistent with competitive-mixture observations.
SN - 2046-2069
ER -