Supramolecular ssDNA templated porphyrin and metalloporphyrin nanoassemblies with tunable helicity

Gevorg Sargsyan, Brian M. Leonard, Jan Kubelka, Milan Balaz

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

Free-base and nickel porphyrin-diaminopurine conjugates were formed by hydrogen-bond directed assembly on single-stranded oligothymidine templates of different lengths into helical multiporphyrin nanoassemblies with highly modular structural and chiroptical properties. Large red-shifts of the Soret band in the UV/Vis spectroscopy confirmed strong electronic coupling among assembled porphyrin-diaminopurine units. Slow annealing rates yielded preferentially right-handed nanostructures, whereas fast annealing yielded left-handed nanostructures. Time-dependent DFT simulations of UV/Vis and CD spectra for model porphyrin clusters templated on the canonical B-DNA and its enantiomeric form, were employed to confirm the origin of observed chiroptical properties and to assign the helicity of porphyrin nanoassemblies. Molar CD and CD anisotropy g factors of dialyzed templated porphyrin nanoassemblies showed very high chiroptical anisotropy. The DNA-templated porphyrin nanoassemblies displayed high thermal and pH stability. The structure and handedness of all assemblies was preserved at temperatures up to +85 °C and pH between 3 and 12. High-resolution transition electron microscopy confirmed formation of DNA-templated nickel(II) porphyrin nanoassemblies and their self-assembly into helical fibrils with micrometer lengths.

Original languageEnglish
Pages (from-to)1878-1892
Number of pages15
JournalChemistry - A European Journal
Volume20
Issue number7
DOIs
Publication statusPublished - 2014 Feb 10

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Metalloporphyrins
Porphyrins
DNA
Nickel
Nanostructures
Anisotropy
Annealing
B-Form DNA
Ultraviolet spectroscopy
Discrete Fourier transforms
Self assembly
Electron microscopy
Hydrogen bonds

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Sargsyan, Gevorg ; Leonard, Brian M. ; Kubelka, Jan ; Balaz, Milan. / Supramolecular ssDNA templated porphyrin and metalloporphyrin nanoassemblies with tunable helicity. In: Chemistry - A European Journal. 2014 ; Vol. 20, No. 7. pp. 1878-1892.
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Supramolecular ssDNA templated porphyrin and metalloporphyrin nanoassemblies with tunable helicity. / Sargsyan, Gevorg; Leonard, Brian M.; Kubelka, Jan; Balaz, Milan.

In: Chemistry - A European Journal, Vol. 20, No. 7, 10.02.2014, p. 1878-1892.

Research output: Contribution to journalArticle

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