title: Metal ion-directed dynamic splicing of DNA through global conformational change by intramolecular complexation.
abstract: Chemically engineered DNAs—in which global conformation can be modulated in response to specific stimuli—could be allosteric functional DNAs themselves or work as a modulator of the functional nucleic acids such as DNAzymes and aptamers. Here, we show that two terpyridines built in the DNA backbone form a stable intramolecular 1:2 complex, [M(terpy)2](2+), with divalent transition metal ions. Upon complexation, the DNA conjugates adopt a Ω-shape structure, in which two distal sequences located outside the terpyridines connect with each other to form a continuous segment with a specific structure or sequence. Such a DNA structure is globally controlled by local metal complexation events that can be rationally designed based on general coordination chemistry. This method is regarded as metal ion-directed dynamic sequence edition or DNA splicing. DNAzymes with peroxidase-like activity can thus be regulated by several transition metal ions through sequence edition techniques based on the Ω-motif.
authors: 1] Department of Applied Chemistry and Biochemistry, Graduate School of Science and Technology, Kumamoto University, 2-39-1 Kurokami, Chuo-ku, Kumamoto 860-8555, Japan [2] CREST, Japan Science and Technology Agency, 7 Gobancho, Chiyoda-ku, Tokyo 102-0076, Japan.
authors: Toshihiro
authors: T
authors: Ihara
authors: Department of Applied Chemistry and Biochemistry, Graduate School of Science and Technology, Kumamoto University, 2-39-1 Kurokami, Chuo-ku, Kumamoto 860-8555, Japan.
authors: Hiroyuki
authors: H
authors: Ohura
authors: Department of Applied Chemistry and Biochemistry, Graduate School of Science and Technology, Kumamoto University, 2-39-1 Kurokami, Chuo-ku, Kumamoto 860-8555, Japan.
authors: Chisato
authors: C
authors: Shirahama
authors: Department of Applied Chemistry and Biochemistry, Graduate School of Science and Technology, Kumamoto University, 2-39-1 Kurokami, Chuo-ku, Kumamoto 860-8555, Japan.
authors: Tomohiro
authors: T
authors: Furuzono
authors: Department of Applied Chemistry and Biochemistry, Graduate School of Science and Technology, Kumamoto University, 2-39-1 Kurokami, Chuo-ku, Kumamoto 860-8555, Japan.
authors: Hiroshi
authors: H
authors: Shimada
authors: Department of Applied Chemistry and Biochemistry, Graduate School of Science and Technology, Kumamoto University, 2-39-1 Kurokami, Chuo-ku, Kumamoto 860-8555, Japan.
authors: Hirotaka
authors: H
authors: Matsuura
authors: 1] Department of Applied Chemistry and Biochemistry, Graduate School of Science and Technology, Kumamoto University, 2-39-1 Kurokami, Chuo-ku, Kumamoto 860-8555, Japan [2] CREST, Japan Science and Technology Agency, 7 Gobancho, Chiyoda-ku, Tokyo 102-0076, Japan.
authors: Yusuke
authors: Y
authors: Kitamura
mesh_terms: D002942:Circular Dichroism; D003300:Copper; D004247:DNA / Q000737:chemistry / Q000378:metabolism*; D021881:DNA, Catalytic / Q000737:chemistry / Q000378:metabolism; D007477:Ions; D007501:Iron; D008670:Metals; D009532:Nickel; D009690:Nucleic Acid Conformation; D011725:Pyridines; D013053:Spectrophotometry; D014466:Ultraviolet Rays; D015032:Zinc
chemical_list: D021881:DNA, Catalytic; D007477:Ions; D008670:Metals; D011725:Pyridines; D003300:Copper; D009532:Nickel; D004247:DNA; D007501:Iron; D015032:Zinc