Introducing structural flexibility into porphyrin–DNA zipper arrays

Brewer, Ashley; Siligardi, Guiliano; Neylon, Cameron; Stulz, Eugen

doi:10.1039/c0ob00535e

Cited by 42 publications

(70 citation statements)

References 47 publications

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“…45 The use of metalated porphyrins is crucial to avoid copper metalation during the coupling; most conveniently zinc is used, which is subsequently lost in the DNA synthesis, yielding the free-base porphyrin–DNA. As alternative methods, amide coupling, 46 click chemistry 47 or maleimide–thiol conjugation 48 can equally well be used. Structurally different modifiers such as diphenyl porphyrin (DPP-dU), tetraphenyl porphyrin (TPP-dU), or propargylamide-linked TPP (TPPA-dU) were thus synthesized (Figure 6a) Phosphitylation is straightforward, though the phosphoramidites are highly susceptible to oxidation due to the photosensitizing activity of the porphyrin.…”

Section: Covalent Attachment Of Porphyrins To Dnamentioning

confidence: 99%

Nanoarchitectonics with Porphyrin Functionalized DNA

Stulz

2017

Acc. Chem. Res.

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105

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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.

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Section: Covalent Attachment Of Porphyrins To Dnamentioning

confidence: 99%

Nanoarchitectonics with Porphyrin Functionalized DNA

Stulz

2017

Acc. Chem. Res.

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105

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“…紫外-可见光谱滴定法是研究卟啉与 DNA 结合能力和作用模式的一种常用方法 [13] , 卟啉 5～12 与 CT DNA 相互作用后, Soret 带均表现明显减色而无红移现象, 且卟啉 5～8 减色更大. 图 3 为卟啉 7 和 11 与 CT DNA 的相互作用, 其中卟啉 7 的 Soret 带减色约 33%, 相同条件下卟啉 11 为 27%, 均大于单体卟啉的减色(＜ 20%), 表明和厚朴酚的引入可能使卟啉 5～12 更易与 DNA 结合, 且卟啉 5～8 相比 9～12 其空间构型更具优势.…”

Section: 卟啉与 Ct Dna 相互作用unclassified

Synthesis and Characterization of Honokiol Bridged Porphyrins as Photosensitizers

Qi-mao¹,

Wang²,

Peng-Xing³

et al. 2012

Chin. J. Org. Chem.

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“…A pair of Por molecules generating exciton‐induced circular dichroism sensitive to the local environment around the Por molecules and secondary structures of DNA can be used as a chiroptical marker . Helical arrays of the Por molecules have been created using DNA as a scaffold . The location and relative alignment of the Por molecules in DNA can be controlled by changing the method of attachment, extrahelical arrangements or embedding into the base pair stack .…”

Section: Introductionmentioning

confidence: 99%

Photoresponsive Electrodes Modified with DNA Duplexes Possessing a Porphyrin Dimer

Takada

Iwaki

Nakamura

et al. 2017

Chemistry A European J

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This work describes the formation of a porphyrin (Por) dimer using a DNA duplex as a scaffold and photocurrent generation from electrodes modified with a monolayer of Por-DNA conjugates. The solid-phase click reaction between an azide-porphyrin and oligonucleotide labeled with an ethynyl group on CPG support was utilized to conjugate the Por to the DNA. UV/Vis absorption and circular dichroism (CD) spectral studies revealed that the Por dimer can be formed through DNA hybridization and that through-space electronic interactions, characterized from the exciton-coupled absorption and the bisignate CD, can occur between the two Por molecules. Photoelectrochemical experiments were performed for the electrodes functionalized with a monolayer composed of the Por-DNA conjugates. It was found that the Por dimer on the electrode, which was designed to resemble the special pair in natural photosynthesis, shows efficient photocurrent generation in the presence of electron-acceptor reagents compared with the Por monomer. These findings strongly support the idea that the DNA structures could be useful to construct Por arrays, which is essential for the design of photo- and bio-electronic devices.

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Introducing structural flexibility into porphyrin–DNA zipper arrays

Cited by 42 publications

References 47 publications

Nanoarchitectonics with Porphyrin Functionalized DNA

Nanoarchitectonics with Porphyrin Functionalized DNA

Synthesis and Characterization of Honokiol Bridged Porphyrins as Photosensitizers

Photoresponsive Electrodes Modified with DNA Duplexes Possessing a Porphyrin Dimer

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