Structural Aspects of Nucleosides: Protonated and Complexed Adenosines

Hauser, Jürg; Keese, Reinhart

doi:10.1002/1522-2675(200208)85:8<2481::aid-hlca2481>3.0.co;2-k

Cited by 4 publications

(2 citation statements)

References 3 publications

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“…35,36 The complex formation of TTFnucleobases with H 2 CNA is expected to cause a CT on the TTF moiety and PT on the nucleobase moiety. In our previous studies on TTF derivatives having imidazole-rings, the robust acidbase H-bonds between the imidazole moiety and anilic acids formed diverse assembled structures.…”

Section: B34mentioning

confidence: 99%

Development of Organic Conductors with Self-Assembled Architectures of Biomolecules: Synthesis and Crystal Structures of Nucleobase-Functionalized Tetrathiafulvalene Derivatives

Murata

Miyazaki

Maki

et al. 2012

Bulletin of the Chemical Society of Japan

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Supramolecular assemblies and charge-transfer complexes of new nucleobase-functionalized tetrathiafulvalene (TTF) derivatives were investigated. Stille-type cross-coupling reaction between tributylstannylated TTF and iodinated nucleobase derivatives yielded mono-and bisnucleobase-substituted TTF derivatives. The electrochemical measurements revealed that the uracil-and cytosine-substituted derivatives possessed strong electron-donating abilities comparable to that of pristine TTF, and the electron-deficient features of adenine and guanine caused high potential shifts of the oxidation waves. In the solution-state electronic spectra, the intramolecular charge-transfer absorption bands were observed at a low-energy region. In the crystal structures, the donor molecules constructed supramolecular polymers by the complementary hydrogen-bonds inherent in nucleobases; a one-dimensional zigzag chain in the adenine-substituted derivative and a linear chain in the bis(uracil)-substituted derivative. The tetracyanoquinodimethane complexes of uraciland cytosine-substituted derivatives possessed a mixed valence state exhibiting high conductivities (room-temperature conductivities = 10). In the cyananilic acid complexes, cytosine-and adenine-substituted TTF acted as electron-donors and proton-acceptors to yield simultaneous charge-and proton-transfer complexes.In the research of conducting charge-transfer (CT) complexes and salts based on tetrathiafulvalene (TTF) and tetracyanoquinodimethane (TCNQ), 1 hydrogen-bond (H-bond) interaction has been utilized as a powerful tool in controlling the molecular arrangement for the construction of effective conduction paths.2,3 From this viewpoint, the self-assembling ability of biological molecules such as amino acids and peptides has been introduced into TTF systems. 4 Complementary Hbonds of nucleobases (Chart 1) are the most important driving force in the formation of DNA duplexes 5 and have been utilized in supramolecular chemistry and crystal engineering. 6,7 The robust and directional H-bonds of nucleobases were also utilized in CT complexes and salts to control the molecular arrangements. The nucleobase-annelated TTF derivatives, of which betainic neutral radicals obtained by the deprotonation of nucleobase moiety and following oxidation of the TTF moiety exhibited high conductivities (room-temperature conductivity (· RT ) = 10 ¹5 10 ¹1 S cm ¹1), formed self-assembled pairs by complementary H-bonds. 8 In protonated cytosinium salts with TCNQ derivatives, the self-assembling ability of hemiprotonated cytosinium by the robust H-bonds constructed segregated TCNQ layers exhibiting high conductivities (· RT = 10 ¹4 10 S cm ¹1 ). 9 Conductive self-supporting films have been also reported in the deoxyguanosine-substituted TTF derivatives under carrier doping with TCNQ (· RT = 10 ¹2 10 ¹3 S cm ¹1 ). 10In addition to these supramolecular aspects of H-bonds, our recent investigations of H-bond-functionalized TTF derivatives revealed the electronic effects of H-bond interactions disclo...

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Section: B34mentioning

confidence: 99%

Development of Organic Conductors with Self-Assembled Architectures of Biomolecules: Synthesis and Crystal Structures of Nucleobase-Functionalized Tetrathiafulvalene Derivatives

Murata

Miyazaki

Maki

et al. 2012

Bulletin of the Chemical Society of Japan

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“…[9][10][11][12][13][14][15][16][17][18][19] Although still rather limited, structural characterization of the protonated forms of the canonical as well as modified DNA and RNA nucleosides is growing. [20][21][22][23][24][25][26][27][28] Knowledge of the structural features of the protonated DNA and RNA nucleosides as the constituents of nucleic acids can be a Department of Chemistry, Wayne State University, Detroit, Michigan 48202, USA.…”

Section: Introductionmentioning

confidence: 99%

Diverse mixtures of 2,4-dihydroxy tautomers and O4 protonated conformers of uridine and 2′-deoxyuridine coexist in the gas phase

Frieler

et al. 2015

Phys. Chem. Chem. Phys.

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The gas-phase conformations of protonated uridine, [Urd+H](+), and its modified form, protonated 2'-deoxyuridine, [dUrd+H](+), generated by electrospray ionization are investigated using infrared multiple photon dissociation (IRMPD) action spectroscopy techniques. IRMPD action spectra of [Urd+H](+) and [dUrd+H](+) are measured over the IR fingerprint and hydrogen-stretching regions. [Urd+H](+) and [dUrd+H](+) exhibit very similar IRMPD spectral profiles. However, the IRMPD yields of [Urd+H](+) exceed those of [dUrd+H](+) in both the IR fingerprint and hydrogen-stretching regions. The measured spectra are compared to the linear IR spectra predicted for the stable low-energy structures of these species computed at the B3LYP/6-311+G(d,p) level of theory to determine the tautomeric conformations populated by electrospray ionization. Both B3LYP and MP2 methods find O4 and O2 protonated canonical as well as 2,4-dihydroxy tautomers among the stable low-energy structures of [Urd+H](+) and [dUrd+H](+). Comparison between the measured IRMPD and calculated linear IR spectra suggests that these species exist in their ring-closed forms and that both 2,4-dihydroxy tautomers as well as O4 protonated canonical conformers coexist in the population generated by electrospray ionization for both [Urd+H](+) and [dUrd+H](+). The 2'-deoxy modification of [dUrd+H](+) reduces the variety of 2,4-dihydroxy tautomers populated in the experiments vs. those of [Urd+H](+).

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Spectral, thermal and optical properties of adenosinium picrate: A nonlinear optical single crystal

Gowri¹,

Devi²,

Sajan³

et al. 2012

Spectrochimica Acta Part A: Molecular and Biomolecular Spectros

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A new organic nonlinear optical material adenosinium picrate (C10H14N5O4+, C6 H2 N3 O7-) was synthesized. The single crystal X-ray diffraction revealed the non-centrosymmetric crystal structure, which is an essential criterion for second harmonic generation. The crystalline nature of the grown crystals was confirmed using powder XRD techniques. Molecular structure was confirmed by NMR spectral analysis and functional groups were identified by FT-IR spectral analysis. The optical transmittance window and the lower cutoff wavelength of the AP have been identified by UV-vis-NIR studies. Thermo gravimetric analysis (TGA) and differential thermal analysis (DTA) were used to study its thermal properties. Powder test with Nd:YAG laser radiation shows second harmonic generation.

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Structural Aspects of Nucleosides: Protonated and Complexed Adenosines

Cited by 4 publications

References 3 publications

Development of Organic Conductors with Self-Assembled Architectures of Biomolecules: Synthesis and Crystal Structures of Nucleobase-Functionalized Tetrathiafulvalene Derivatives

Development of Organic Conductors with Self-Assembled Architectures of Biomolecules: Synthesis and Crystal Structures of Nucleobase-Functionalized Tetrathiafulvalene Derivatives

Diverse mixtures of 2,4-dihydroxy tautomers and O4 protonated conformers of uridine and 2′-deoxyuridine coexist in the gas phase

Spectral, thermal and optical properties of adenosinium picrate: A nonlinear optical single crystal

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