Abstract

Abstract The efficiency and dynamics of hole transport via base mismatches and strand crossings have been determined for 10 DNA hairpins by means of femtosecond transient absorption spectroscopy. The hairpins possess a stilbenedicarboxamide hole donor and stilbenediether hole acceptor separated by seven base pairs. Hole transport occurs via an intra- or interstrand A 3 G 4 diblock purine sequence that contains either a single base pair mismatch or strand crossing. Pyrimidine-pyrimidine mismatches (TT or CC) effectively block intrastrand hole transport; whereas purine-purine mismatches (AA or GG) permit efficient interstrand hole transport. Purine-to-purine intrastrand hole transport between adjacent matched base pairs is also moderately efficient (AG > AA > GG). Based upon these results AA mismatches are being employed in the design of three-way junctions for incorporation in prototype charge splitting and charge combining devices.

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