Preparation of 1‐Ethynylpyrene‐Modified DNA via Sonogashira‐Type Solid‐Phase Couplings and Characterization of the Fluorescence Properties for Electron‐Transfer Studies

Rist, M; Amann, Nicole; Wagenknecht, Hans‐Achim

doi:10.1002/ejoc.200300125

Cited by 72 publications

(61 citation statements)

References 54 publications

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“…It was found in studies of 1-ethynylpyrene-modified uracil incorporated into DNA that the strength of the 405 nm pyrene absorption band can be mainly correlated to the strength of the base-stacking interaction with the neighbouring bases. [43,46] Compared to the DNA systems presented in this reference, the effects monitored in our study are relatively small. A reason for this might be found in the generally lower stability of RNA, which leads to weaker stacking interactions.…”

Section: Fluorescence Spectramentioning

confidence: 83%

“…[43] It is absent, however, if a direct linker between pyrene and base is used as monitored by Amann et al [44] The shift therefore has to be attributed to the presence of both the acetylene linker and the base in combination. Similar effects have also been reported for cyanine dye systems by Fegan et al employing an ethynyl linker.…”

Section: Absorption Spectramentioning

confidence: 99%

“…[42] The central emission wavelength of the singly modified duplexes is red-shifted by roughly 35 nm (444-467 nm) with respect to the chromophore, and the fluorescence spectrum is in good accordance with previous studies on similar systems. [32,43,46] These strong changes have been attributed to strong coupling of the dye to the base; this results in an intramolecular exciplex with an at least partial charge transfer from the pyrene to the adenine. [15,[47][48][49][50] The strength of this exciplex coupling is strongly dependent on the attachment site of the pyrene to the base.…”

Section: Fluorescence Spectramentioning

confidence: 99%

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2‐(1‐Ethynylpyrene)‐Adenosine as a Folding Probe for RNA—Pyrene in or out

et al. 2010

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A series of short RNA duplexes containing one or two 1-ethynylpyrene-modified adenine bases was synthesised. The melting behaviour of these duplexes was examined by monitoring temperature-dependent pyrene fluorescence. In the singly modified RNA duplexes, the bases flanking the ethynylpyrene-rA were varied to examine the sequence specificity of the fluorescence change of pyrene upon RNA hybridisation. Because an increase in pyrene fluorescence upon melting of the duplex can be correlated with intercalation of pyrene, and a decrease is usually associated with the position of pyrene outside the strand, a relationship between the flanking bases and the tendency of the dye to intercalate has been established. It was found that pyrene intercalation is less likely to take place if the modified base is flanked only by A-U base pairs. Flanking G-C base pairs, even only in the 5'-direction of the modified base, will favour intercalation. In addition, we examined a doubly modified compound that had a pyrene located on each strand. The spectra indicated that the two pyrenes were close enough for interaction. Upon melting of the strand, a fluorescence blue shift corresponding to the dissociation of the pyrene-pyrene complex could be observed in addition to the intensity effect already known from the singly modified compounds. Two melting curves based on the different properties of the fluorophore could be extracted, leading to different melting points corresponding to the global duplex melting and to the change of local pyrene environment, respectively.

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Section: Fluorescence Spectramentioning

confidence: 83%

Section: Absorption Spectramentioning

confidence: 99%

Section: Fluorescence Spectramentioning

confidence: 99%

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2‐(1‐Ethynylpyrene)‐Adenosine as a Folding Probe for RNA—Pyrene in or out

et al. 2010

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“…We predict alkyne-alkyne coupling will become increasingly popular. Notable examples include (i) the preparation of 1-ethynylpyrene-modified oligonucleotides using Sonogashiratype cross-coupling conditions on controlled pore glasses, 166 (ii) Cadiot-Chodkiewicz coupling of (triisopropylsilyl)-protected bromoacetylene and alkyne-terminated selfassembled monolayers of alkanethiolate on gold, 167 (iii) the work of Bedzyk and co-workers detailing the use of microwave-assisted Sonogashira reactions, 168 and more recently (iv) the report by Gooding and co-workers on the Hay catalytic system [CuCl, N,N,N 0 ,N 0 -tetramethylethylenediamine] under non-stringent oxidative conditions to bridge ferrocenyl units to passivating alkenyl Si(100) monolayers through a 1,3-diyne (-CRC-CRC-) linker. 169 …”

Section: Acetylenic Couplingmentioning

confidence: 99%

The molecular level modification of surfaces: from self-assembled monolayers to complex molecular assemblies

2011

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The modification of surfaces with self-assembled monolayers (SAMs) containing multiple different molecules, or containing molecules with multiple different functional components, or both, has become increasingly popular over the last two decades. This explosion of interest is primarily related to the ability to control the modification of interfaces with something approaching molecular level control and to the ability to characterise the molecular constructs by which the surface is modified. Over this time the level of sophistication of molecular constructs, and the level of knowledge related to how to fabricate molecular constructs on surfaces have advanced enormously. This critical review aims to guide researchers interested in modifying surfaces with a high degree of control to the use of organic layers. Highlighted are some of the issues to consider when working with SAMs, as well as some of the lessons learnt (169 references). 2011 The Royal Society of Chemistry. The modification of surfaces with self-assembled monolayers (SAMs) containing multiple different molecules, or containing molecules with multiple different functional components, or both, has become increasingly popular over the last two decades. This explosion of interest is primarily related to the ability to control the modification of interfaces with something approaching molecular level control and to the ability to characterise the molecular constructs by which the surface is modified. Over this time the level of sophistication of molecular constructs, and the level of knowledge related to how to fabricate molecular constructs on surfaces have advanced enormously. This critical review aims to guide researchers interested in modifying surfaces with a high degree of control to the use of organic layers. Highlighted are some of the issues to consider when working with SAMs, as well as some of the lessons learnt (169 references).

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“…On the other hand, the pyrene marker has been used widely to investigate electron injection into DNA strands and has proven helpful in this context [9,10]. Synthesis of a pyrene-adenine compound and its application in RNA unfolding studies has been reported recently [11].…”

Section: Introductionmentioning

confidence: 99%