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A photocaged diene is introduced at the 5′-end of oligonucleotides using the H-phosphonate approach. The photoenol-functionalized DNA is subsequently employed for the conjugation to a protein and the spatially controlled immobilization onto surfaces using a light-induced Diels–Alder cycloaddition. Fully functional protein–DNA conjugates and patterned DNA surfaces are obtained under mild irradiation conditions.doi:10.5445/ir/1000053003 fatcat:n6x7tasxs5a6zk2icqr3icmfnq