Nanoarchitectonics with Porphyrin Functionalized DNA

Abstract

ConspectusDNA is well-known as bearer of the genetic code. Since its structure elucidation nearly seven decades ago by Watson, Crick, Wilkins, and Franklin, much has been learned about its detailed structure, function, and genetic coding. The development of automated solid-phase synthesis, and with it the availability of synthetic DNA with any desired sequence in lengths of up to hundreds of bases in the best case, has contributed much to the advancement of the field of DNA research. In addition, classic organic synthesis has allowed introduction of a very large number of modifications in the DNA in a sequence specific manner, which have initially been targeted at altering the biological function of DNA. However, in recent years DNA has become a very attractive scaffold in supramolecular chemistry, where DNA is taken out of its biological role and serves as both stick and glue molecule to assemble novel functional structures with nanometer precision. The attachment of functionalities to DNA has led to the creation of supramolecular systems with applications in light harvesting, energy and electron transfer, sensing, and catalysis. Functional DNA is clearly having a significant impact in the field of bioinspired nanosystems.Of particular interest is the use of porphyrins in supramolecular chemistry and bionanotechnology, because they are excellent functional groups due to their electronic properties that can be tailored through chemical modifications of the aromatic core or through insertion of almost any metal of the periodic table into the central cavity. The porphyrins can be attached either to the nucleobase, to the phosphate group, or to the ribose moiety. Additionally, noncovalent templating through Watson–Crick base pairing forms an alternative and attractive approach. With this, the combination of two seemingly simple molecules gives rise to a highly complex system with unprecedented possibilities for modulation of function, and with it applications, particularly when combined with other functional groups. Here, an overview is given on the developments of using porphyrin modified DNA for the construction of functional assemblies. Strategies for the synthesis and characterization are presented alongside selected applications where the porphyrin modification has proven to be particularly useful and superior to other modifiers but also has revealed its limitations. We also discuss implications on properties and behavior of the porphyrin–DNA, where similar issues could arise when using other hydrophobic and bulky substituents on DNA. This includes particularly problems regarding synthesis of the building blocks, DNA synthesis, yields, solubility, and intermolecular interactions.

Materials Nanoarchitectonics as Cell Regulators

“…Therefore, applications of the nanoarchitectonics concept to bio‐related science and technology have increasingly attracted research attentions . For example, Stulz described the nanoarchitectonics strategy for the construction of functional assemblies using porphyrin modified DNA in his Account article . Peptide‐based nanoarchitectonics was discussed by Yan and co‐workers who summarized applications of self‐assembled peptide nanoarchitectures in biomimetic photosystems, optical waveguiding by assembled peptide microtubes, and phototherapy .…”

Oxidation catalysis by iron and manganese porphyrins within enzyme‐like cages

“…Even though peptides and proteins are Nature's favorite building blocks for modulating metalloporphyrin reactivity, there is still room for further innovation. Several macromolecules and/or supramolecular systems have been used so far for the development of metalloporphyrin conjugates with different properties . Among them, we will report, in Section 6, the innovative strategies based on the construction of metalloporphyrin‐based metal‐organic frameworks (MOF) .…”

Photoresponsive Electrodes Modified with DNA Duplexes Possessing a Porphyrin Dimer

“…Among the various types of functional chromophores, porphyrin (Por) molecules are especially fascinating because of their various photochemical properties such as outstanding energy‐ and electron‐transfer properties, light‐harvesting, optics, and catalysis . Therefore, several research groups have reported the preparation of Por‐conjugated DNA derivatives by using various synthetic approaches . Conventional phosphoroamidite chemistry for the modification has been successfully applied to synthesize Por–DNA conjugates .…”

“…The photophysical and optical characteristics of Por molecules can be exploited to investigate the structural aspects of DNA and to create functional DNA nanostructures . Long‐range exciton coupling between the Por molecules placed at a specific distance on the DNA has been demonstrated .…”

“…[9][10][11] Therefore, several research groups have reported the preparation of Por-conjugated DNA derivatives by using variouss ynthetic approaches. [12] Conventional phosphoroamidite chemistry for the modification has been successfully applied to synthesize Por-DNA conjugates. [13][14][15] Post-synthetic modifications, such as the condensationr eactiona nd click reactions, were used for the covalentconjugation of DNA with porphyrin.…”