title: Light-driven DNA nanomachine with a photoresponsive molecular engine.
abstract: CONSPECTUS: DNA is regarded as an excellent nanomaterial due to its supramolecular property of duplex formation through A-T and G-C complementary pairs. By simply designing sequences, we can create any desired 2D or 3D nanoarchitecture with DNA. Based on these nanoarchitectures, motional DNA-based nanomachines have also been developed. Most of the nanomachines require molecular fuels to drive them. Typically, a toehold exchange reaction is applied with a complementary DNA strand as a fuel. However, repetitive operation of the machines accumulates waste DNA duplexes in the solution that gradually deteriorate the motional efficiency. Hence, we are facing an "environmental problem" even in the nanoworld. One of the direct solutions to this problem is to use clean energy, such as light. Since light does not contaminate the reaction system, a DNA nanomachine run by a photon engine can overcome the drawback of waste that is a problem with molecular-fueled engines. There are several photoresponsive molecules that convert light energy to mechanical motion through the change of geometry of the molecules; these include spiropyran, diarylethene, stilbene, and azobenzene. Although each molecule has both advantages and drawbacks, azobenzene derivatives are widely used as "molecular photon engines". In this Account, we review light-driven DNA nanomachines mainly focusing on the photoresponsive DNAs that we have developed for the past decade. The basis of our method is installation of an azobenzene into a DNA sequence through a d-threoninol scaffold. Reversible hybridization of the DNA duplex, triggered by trans-cis isomerization of azobenzene in the DNA sequences by irradiation with light, induces mechanical motion of the DNA nanomachine. Moreover we have successfully developed azobenzene derivatives that improve its photoisomerizaition properties. Use of these derivatives and techniques have allowed us to design various DNA machines that demonstrate sophisticated motion in response to lights of different wavelengths without a drop in photoregulatory efficiency. In this Account, we emphasize the advantages of our methods including (1) ease of preparation, (2) comprehensive sequence design of azobenzene-tethered DNA, (3) efficient photoisomerization, and (4) reversible photocontrol of hybridization by irradiation with appropriate wavelengths of light. We believe that photon-fueled DNA nanomachines driven by azobenzene-derivative molecular photon-fueled engines will be soon science rather than "science fiction".
authors.affiliation: Graduate School of Engineering, Nagoya University , Furo-cho, Chikusa-ku, Nagoya 464-8603 Japan.
authors.forename: Yukiko
authors.initials: Y
authors.lastname: Kamiya
authors.forename: Hiroyuki
authors.initials: H
authors.lastname: Asanuma
mesh_terms: D000605:Amino Alcohols / Q000737:chemistry; D001391:Azo Compounds / Q000737:chemistry*; D002072:Butylene Glycols / Q000737:chemistry; D060326:Chemistry Techniques, Synthetic; D004247:DNA / Q000138:chemical synthesis / Q000737:chemistry*; D007536:Isomerism; D008027:Light; D049329:Nanostructures / Q000737:chemistry*; D009690:Nucleic Acid Conformation; D010777:Photochemistry / Q000379:methods*; D017785:Photons
chemical_list: D000605:Amino Alcohols; D001391:Azo Compounds; D002072:Butylene Glycols; C532652:threoninol; D004247:DNA; C009850:azobenzene