Precise control over the valency of quantum dots (QDs) is critical and fundamental for quantitative imaging in living cells. However, prior approaches on valence control of QDs remain restricted to single types of valences. A DNA-programmed general strategy is presented for valence engineering of QDs with high modularity and high yield. By employing a series of programmable DNA scaffolds, QDs were generated with tunable valences in a single step with near-quantitative yield (>95 %). The use of these valence-engineered QDs was further demonstrated to develop 12 types of topologically organized QDs-QDs and QDs-AuNPs and 4 types of fluorescent resonance energy transfer (FRET) nanostructures. Quantitative analysis of the FRET nanostructures and live-cell imaging reveal the high potential of these nanoprobes in bioimaging and nanophotonic applications.
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