Tadao Takada

Sequence dependence of excess electron transfer in DNA.

DNA-mediated charge transfer has recently received a substantial attention because of its biological relevance in the DNA damage and DNA repair as well as the potential applications to nanoscale electronic devices. In contrast to the numerous mechanistic studies on oxidative hole transfer (HT) through DNA, our understanding of reductive electron transfer process still remains limited. In this article, we demonstrate the results of direct observation of the excess electron transfer (EET) through DNA, which conjugated with aminopyrene ((A)Py) and diphenylacetylene (DPA) as a photosensitizing donor and an acceptor of excess electron, respectively. By inserting dihydrothymine as a spacer between (A)Py and T or C, the yield of electron arrival to DPA was improved. It was indicated that EET through DNA completed within a few or a few tens nanosecond time scale even for EET over 34 Å for both consecutive T and C sequences. The various factors such as mismatch sequence and DNA length on the yield of electron arrival to DPA were examined.

Photocurrent Generation Enhanced by Charge Delocalization over Stacked Perylenediimide Chromophores Assembled within DNA

We now report the photocurrent generation and charge transfer dynamics of stacked perylenediimide (PDI) molecules within a π-stack array of DNA. The cofacially stacked PDI dimer and trimer were found to strongly enhance the photocurrent generation compared to an isolated PDI monomer. Femtosecond time-resolved transient absorption experiments revealed that the excitation of the stacked PDI dimer and trimer provided the broad transient absorption band, which was attributed to the charge delocalization of a negative charge over the PDI chromophores. The lifetime of the charge delocalization of the PDI dimer and trimer (nearly 1 ns) was much longer than that of the charge separated state of the PDI monomer. A comparison between the photocurrent measurements and time-resolved transient absorption measurements demonstrated that the cofacially stacked structure could possibly lead to the charge delocalization and increase the lifetime of the charge-separated state that is essential to enhancing the photocurrent generation.

DNA-templated assembly of naphthalenediimide arrays.

π-Stacked naphthalenediimide (NDI) arrays are of interest as charge-transport materials. We have designed and synthesized an NDI derivative with two Zn(II)-cyclens that act as receptors for the thymine base in DNA. UV/Vis and CD spectroscopy, gel filtration, and molecular-modeling studies have shown that the bis(Zn(II)-cyclen)-NDI can be assembled in the presence of oligo-dT to form π-stacked NDI arrays. The assembly of the NDI arrays was found to be dependent on the length of the oligo-dT and the temperature. The NDI-oligo-dT assembly on a gold substrate exhibits photocurrent responses due to electron transfer through the π-stacked array.

Molecular Arrangement and Assembly Guided by Hydrophobic Cavities inside DNA

DNA is a unique yet useful material to organize nanoscale molecular arrays along the helix axis. In this study, we demonstrate a useful approach for creating molecular arrays inside a double helical DNA. Our approach is based on a host-guest system. Introducing abasic sites into DNA afforded a hydrophobic cavity that serves as a host. A planar aromatic molecule (cationic perylenediimide, PDI) was used as the guest molecule. In an aqueous solution, the PDI molecules tend to aggregate with themselves due to the strong hydrophobicity. In the presence of DNA with the cavity, the binding of the PDI was found to site-specifically occur in the hydrophobic cavity. The unique assembly and arrangement for more than two PDI molecules was achieved by controlling the sizes and positions of the cavities. Our approach would provide a simple and convenient way to construct one-dimensional aromatic arrays in DNA.

Photocurrent Generation through Charge-Transfer Processes in Noncovalent Perylenediimide/DNA Complexes

The charge-transfer process in noncovalent perylenediimide (PDI)/DNA complexes has been investigated by using nanosecond laser flash photolysis (LFP) and photocurrent measurements. The PDI/DNA complexes were prepared by inclusion of cationic PDI molecules into the artificial cavities created inside DNA. The LFP experiments showed that placement of the PDI chromophore at a specific site and included within the base stack of DNA led to the efficient generation of a charge-separated state with a long lifetime by photoexcitation. When two PDI chromophores were separately placed at different positions in DNA, the yield of the charge-separated state with a long lifetime was dependent upon the number of A-T base pairs between the PDIs, which was explained by electron hopping from one PDI to another. Photocurrent generation of the DNA-modified electrodes with the complex was also dependent upon the arrangement of the PDI chromophores. A good correlation was obtained between observed charge separation and photocurrent generation on the PDI/DNA-modified electrodes, which demonstrated the importance of the defined arrangement and assembly of organic chromophores in DNA for efficient charge separation and transfer in multichromophore arrays.

Cationic perylenediimide as a specific fluorescent binder to mismatch containing DNA

Small ligand molecules, which can recognize thermodynamically unstable site within DNA, such as mismatch base pair, abasic site, and single-bulge, have attracted much attention because of their potential diagnostics and biological applications. In this paper, we describe the binding of cationic perylenediimide (cPDI) molecules to thymine-containing mismatch base pair in DNA and the formation of cPDI dimer at the mismatch site. The cPDI dimer exhibits a characteristic excimer emission at 650nm. For T/T mismatch containing DNA, the switching behavior from the PDI dimer (650nm) to the monomer (550nm) emission in specific response to Hg(2+) ion was observed.

Diketopyrrolopyrrole J-Aggregates Formed by Self-Organization with DNA

Bis(2-thienyl)diketopyrrolopyrrole with two Zn(II)-cyclens (ZnCyc-DPP) was designed and synthesized to evaluate the selective binding of Zn(II)-cyclen with thymine base in single-strand DNA as a tool for the construction of a highly ordered multichromophore system on DNAs. Through UV/Vis titrations, gel filtration chromatography, and circular dichroism spectroscopy, ZnCyc-DPP formed J-type DPP aggregates with oligo-dTn DNAs. The DPP aggregates absorbed on a gold electrode exhibited good photocurrent responses. The present results show that binding Zn(II)-cyclen-chromophore conjugates and thymine bases together is a powerful tool for preparing DNA-templated multichromophoric systems with specific functions.

Electrical Property of DNA Field-Effect Transistor: Charge Retention Property

We discovered the charge retention property of the field-effect transistor (FET) in a Si gate/SiO2/DNA channel structure. The DNA FET with the Si source and drain showed hole conduction, and the drain current was controlled by the gate voltage application. In addition, the experimental results that currents similar to the space change limited currents (SCLCs) and hysteresis were observed in the drain current–drain voltage (Id–Vd) characteristics indicate that the negative charges captured at the trap sites in the DNA enhance the hole currents. Also, the drain currents increased as the repetition number of the measurement increased. However, by inserting the refresh process of gate voltage application of -50 V between each measurement, the current increase was restrained. This phenomenon indicates that the trap and detrap process of electrons occurs in the DNA channel depending on the gate voltage application. The charge retention mechanism was also discussed.

Donor–Acceptor Heterojunction Configurations Based on DNA–Multichromophore Arrays

Multichromophore arrays of bis(2-thienyl)diketopyrrolopyrrole (DPP) and naphthalenediimide (NDI) with two Zn(II) -cyclens were constructed using thymidine DNA as a scaffold through the binding of the Zn(II) -cyclens with thymine bases. We demonstrate photocurrent generation in a donor-acceptor heterojunction configuration consisting of the DPP (donor) and NDI (acceptor) arrays co-immobilized on an Au electrode. The co-immobilized electrode exhibited good photocurrent responses because of the efficient charge separation between the DPP and NDI arrays. In contrast, an immobilized electrode consisting of randomly assembled DPP-NDI arrays generated no photocurrent response because DPP formed ground-state charge-transfer complexes with NDI in the randomly assembled arrays. Therefore, our approach to generate donor-acceptor heterojunctions based on DNA-multichromophore arrays is a useful method to efficiently generate photocurrent.

Study of charge retention mechanism for DNA memory FET

The charge retention mechanism of the λ-DNA molecules with 400 bp (136 nm) are examined. The DNA solution was dropped on the Si source and drain electrodes with the gap of 120 nm. The change of the refresh characteristics by applying the negative voltage to the gate was measured. As a result, it was found that the electron trap remarkably influenced on the hole conduction of the DNA channel. In addition, the DNA has memory ability because the trap and detrap of the electrons can be controlled by the refresh voltage.