RESUMEN
π-Conjugated molecules are viewed as fundamental components in forthcoming molecular nanoelectronics in which semiconducting functional units are linked to each other via metallic molecular wires. However, it is still challenging to construct such block cooligomers on the surface. Here, we present a synthesis of [18]-polyene-linked Zn-porphyrin cooligomers via a two-step reaction of the alkyl groups on Cu(111) and Cu(110). Nonyl groups (-C9H19) substituted at the 5,15-meso positions of Zn-porphyrin were first transformed to alkenyl groups (-C9H10) by dehydrogenation. Subsequently, homocoupling of the terminal -CH2 groups resulted in the formation of extended [18]-polyene-linked porphyrin cooligomers. The structures of the products at each reaction step were investigated by bond-resolved scanning tunneling microscopy at low temperatures. A combination of angle-resolved photoemission spectroscopy and density functional theory calculations revealed the metallic property of the all trans [18]-polyene linker on Cu(110). This finding may provide an approach to fabricate complex nanocarbon structures on the surface.
RESUMEN
Non-canonical protonation at cytosine (C) in DNA is related to a formation of second order DNA structures such as i-motif, which has a role in gene regulation. Although the detailed structural information is indispensable for comprehension of their functions in cells, the protonation status of C in complicated environments is still elusive. To provide a reporter system of non-canonical protonation, we focused on the molecular vibration that could be monitored using the Raman spectroscopy. We prepared a cytosine derivative (PC) with an acetylene unit as a Raman tag, and found that the Raman signal of acetylene in PC in oligodeoxynucleotides (ODNs) changed due to protonation at the cytosine ring which shortened an acetylene bond. The signal change in i-motif-forming ODNs was also observed in crowded environments with polyethylene glycol, evidencing protonation in i-motif DNA in complicated environments. This system would be one of tracking tools for protonation in DNA structures.
