TY - JOUR
T1 - Control of biocatalytic transformations by programmed DNA assemblies
AU - Freeman, Ronit
AU - Sharon, Etery
AU - Teller, Carsten
AU - Willner, Itamar
PY - 2010/3/22
Y1 - 2010/3/22
N2 - This study demonstrates the self-assembly of inhibitor/enzyme-tethered nucleic acid fragments or enzyme I-, enzyme II-modified nucleic acids into functional nanostructures that lead to the controlled inhibition of the enzyme or the activation of an enzyme cascade. In one system, the anti-cocaine aptamer subunits are modified with monocarboxy methylene blue (MB+) as the inhibitor and with choline oxidase (ChOx). The cocaine-induced self-assembly of the aptamer subunits complex results in the inhibition of ChOx by MB +. In a further configuration, two nucleic acids of limited complementarity are functionalized at their 3′ and 5′ ends with glucose oxidase (GOx) and horseradish peroxidase (HRP), respectively, or with MB+ and ChOx. In the presence of a target DNA sequence, synergistic complementary base-pairing occurs, thus leading to stable supramolecular Yshaped nanostructures of the nucleic acid units. A GOx/HRP bienzyme cascade or the programmed inhibition of ChOx by MB+ is demonstrated in the resulting nucleic acid nanostructures. A quantitative theoretical model that describes the nucleic acid assemblies and that results in the inhibition of ChOx by MB+ or in the activation of the GOx/HRP cascade, respectively, is provided.
AB - This study demonstrates the self-assembly of inhibitor/enzyme-tethered nucleic acid fragments or enzyme I-, enzyme II-modified nucleic acids into functional nanostructures that lead to the controlled inhibition of the enzyme or the activation of an enzyme cascade. In one system, the anti-cocaine aptamer subunits are modified with monocarboxy methylene blue (MB+) as the inhibitor and with choline oxidase (ChOx). The cocaine-induced self-assembly of the aptamer subunits complex results in the inhibition of ChOx by MB +. In a further configuration, two nucleic acids of limited complementarity are functionalized at their 3′ and 5′ ends with glucose oxidase (GOx) and horseradish peroxidase (HRP), respectively, or with MB+ and ChOx. In the presence of a target DNA sequence, synergistic complementary base-pairing occurs, thus leading to stable supramolecular Yshaped nanostructures of the nucleic acid units. A GOx/HRP bienzyme cascade or the programmed inhibition of ChOx by MB+ is demonstrated in the resulting nucleic acid nanostructures. A quantitative theoretical model that describes the nucleic acid assemblies and that results in the inhibition of ChOx by MB+ or in the activation of the GOx/HRP cascade, respectively, is provided.
KW - Aptamers
KW - Cocaine
KW - DNA
KW - Enzymes
KW - Inhibitors
UR - http://www.scopus.com/inward/record.url?scp=77949723931&partnerID=8YFLogxK
U2 - 10.1002/chem.200902559
DO - 10.1002/chem.200902559
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C2 - 20151432
AN - SCOPUS:77949723931
SN - 0947-6539
VL - 16
SP - 3690
EP - 3698
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 12
ER -