Synthesis and Properties of 2'-Deoxyuridine Analogues Bearing Various Azobenzene Derivatives at the C5 Position

Mori, Shohei; Morihiro, Kunihiko; Kasahara, Yuuya; Tsunoda, Shin‐ichi; Obika, Satoshi

doi:10.3390/chemosensors3020036

Cited by 6 publications

(9 citation statements)

References 28 publications

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“…124 Diversification of the azobenzenes did not lead to a significant increase in DT m . 125 Using LNAs, a DT m of 17 1C could be achieved, but only with the inclusion of three azobenzene-modified locked uridine units into a 12 bp DNA/RNA hybrid. Installation of a single azobenzene modified LNA led to a DT m of 3 1C.…”

Section: Effect Of Photoswitches Attached To Nucleosides On Duplex Stabilitymentioning

confidence: 99%

Recent developments in reversible photoregulation of oligonucleotide structure and function

2017

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There is a growing interest in the photoregulation of biological functions, due to the high level of spatiotemporal precision achievable with light. Additionally, light is non-invasive and waste-free. In particular, the photoregulation of oligonucleotide structure and function is a rapidly developing study field with relevance to biological, physical and material sciences. Molecular photoswitches have been incorporated in oligonucleotides for 20 years, and the field has currently grown beyond fundamental studies on photochemistry of the switches and DNA duplex stability, and is moving towards applications in chemical biology, nanotechnology and material science. Moreover, the currently emerging field of photopharmacology indicates the relevance of photocontrol in future medicine. In recent years, a large number of publications has appeared on photoregulation of DNA and RNA structure and function. New strategies are evaluated and novel, exciting applications are shown. In this comprehensive review, the key strategies for photoswitch inclusion in oligonucleotides are presented and illustrated with recent examples. Additionally the applications that have emerged in recent years are discussed, including gene regulation, drug delivery and materials design. Finally, we identify the challenges that the field currently faces and look forward to future applications.

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Section: Effect Of Photoswitches Attached To Nucleosides On Duplex Stabilitymentioning

confidence: 99%

Recent developments in reversible photoregulation of oligonucleotide structure and function

2017

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“…43 This property may be an advantage for photo-pharmacology with a controlled half-life. 49 The photo-and thermo-isomerization properties of LNA-U Az were similar to that of dU Az ; 34,35 thus, the rigidity of the sugar moiety does not affect the trans-cis isomerization properties of the azobenzene unit.…”

Section: Isomerization Properties Of Lna-u Az In Onmentioning

confidence: 86%

“…Functionalization of the C5-position of the pyrimidine nucleobase via a rigid alkyne linker is particularly interesting as it enables predictable positioning of functional moieties in the major groove of nucleic acid duplexes. For example, 2′-deoxyuridine analogues functionalized with C5-fluorophores, [12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30] C5redox labels 31,32 and C5-photochromic compounds [33][34][35] have been reported. Recently, Hrdlicka et al combined sugar-and nucleobase-modifications and developed C5-functionalized LNA uridine (U) derivatives with various functional groups via an alkyne linker.…”

Section: Introductionmentioning

confidence: 99%

“…1). 34,35 Azobenzene and its derivatives are widely used for photo-switching in biomolecules because of their efficient photo-isomerization properties and resulting dynamic changes in the geometry and dipole moment. [42][43][44] dU Az in ONs was photo-isomerized from the trans-to cis-form with an efficiency of 60% by irradiation at 365 nm and from the cis-to trans-form with an efficiency of 80% by irradiation at 450 nm.…”

Section: Introductionmentioning

confidence: 99%

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C5-azobenzene-functionalized locked nucleic acid uridine: isomerization properties, hybridization ability, and enzymatic stability

et al. 2015

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Oligonucleotides (ONs) modified with a locked nucleic acid (LNA) are widely used in the fields of therapeutics, diagnosis, and nanotechnology. There have been significant efforts towards developing LNA analogues bearing modified bridges to improve their hybridization ability, nuclease resistance, and pharmacokinetic profiles. Moreover, nucleobase modifications of LNA are useful strategies for the functionalization of ONs. Modifications of the C5-position of pyrimidine nucleobases are particularly interesting because they enable predictable positioning of functional groups in the major groove of the duplex. Here we report the synthesis of C5-azobenzene-functionalized LNA uridine (LNA-U(Az)) and properties of LNA-U(Az)-modified ONs, including isomerization properties, hybridization ability, and enzyme stability. LNA-U(Az) in ON is photo-isomerized effectively and reversibly by irradiation at 365 nm (trans to cis) and 450 nm (cis to trans). LNA-U(Az)-modified ONs show RNA-selective hybridization ability despite the large hydrophobic azobenzene moiety extending into the major groove of the duplex. The enzymatic stability of LNA-U(Az)-modified ONs is higher than that of natural and LNA-modified ONs with or without photo-irradiation. Our results indicate that LNA-U(Az) holds promise for RNA targeting and photo-switchable technologies.

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“…attached the azobenzene moiety to the 5‐position of uridine using an alkyne linker [41a] . This led to an improved PSS under UV‐irradiation (PSS UV ) of 60 % and PSS under visible light (PSS vis ) of 80 % with a thermal half‐life of the cis ‐isomer of 44 minutes [63] . However, the impact on the melting temperature of DNA was rather low, ranging up to 5 °C.…”

Section: Structure‐function Relationships Of Pcnsmentioning

confidence: 99%

Photochromic Nucleosides and Oligonucleotides

Bargstedt,

Reinschmidt,

Tydecks

et al. 2023

Angew Chem Int Ed

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Photochromism is a reversible phenomenon wherein a material undergoes a change in color upon exposure to light. In organic photochromes, this effect often results from light‐induced isomerization reactions, leading to alterations in either the spatial orientation or electronic properties of the photochrome. The incorporation of photochromic moieties into biomolecules, such as proteins or nucleic acids, has become a prevalent approach to render these biomolecules responsive to light stimuli. Utilizing light as a trigger for the manipulation of biomolecular structure and function offers numerous advantages compared to other stimuli, such as chemical or electrical treatments, due to its non‐invasive nature. Consequently, light proves particularly advantageous in cellular and tissue applications. In this review, we emphasize recent advancements in the field of photochromic nucleosides and oligonucleotides. We provide an overview of the design principles of different classes of photochromes, synthetic strategies, critical analytical challenges, as well as structure‐property relationships. The applications of photochromic nucleic acid derivatives encompass diverse domains, ranging from the precise photoregulation of gene expression to the controlled modulation of the three‐dimensional structures of oligonucleotides and the development of DNA‐based fluorescence modulators. Moreover, we present a future perspective on potential modifications and applications.

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Synthesis and Properties of 2'-Deoxyuridine Analogues Bearing Various Azobenzene Derivatives at the C5 Position

Cited by 6 publications

References 28 publications

Recent developments in reversible photoregulation of oligonucleotide structure and function

Recent developments in reversible photoregulation of oligonucleotide structure and function

C5-azobenzene-functionalized locked nucleic acid uridine: isomerization properties, hybridization ability, and enzymatic stability

Photochromic Nucleosides and Oligonucleotides

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