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Linker-mediated aggregation plays an important role in modern nanoscience. We demonstrate that it departs sharply from classical Smoluchowski kinetics because cluster reactivity evolves during growth. Combining theory with DNA-linked gold-nanoparticle experiments, we establish kinetic critical point controlled by linker abundance. Below threshold, active linkers are depleted and growth arrests; above threshold, clusters accumulate reactive sites, self-accelerate, and cross over to diffusion-limited coarsening. Experiments verify the predicted arrest, accelerated growth, and scaling collapse.

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