Photoinduced Addition of Glycosyl Thiols to Alkynyl Peptides: Use of Free-Radical Thiol−Yne Coupling for Post-Translational Double-Glycosylation of Peptides

Conte, Mauro Lo; Pacifico, Salvatore; Marra, Alberto; Dondoni, Alessandro

doi:10.1021/jo1008178

Cited by 90 publications

(46 citation statements)

References 42 publications

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“…This is even true for cases where the thiol–yne click reaction is considered to be highly efficient. Previous studies suggested that the reaction rate of the second step in the thiol–yne reaction is must faster than that of the first step 35. The glycosylation process, in our cases, showed that some of the alkyne groups have only undergone the first step.…”

Section: Resultssupporting

confidence: 50%

Controllable glycosylation of polyphosphazene via radical thiol–yne click chemistry

Ren

Huang

et al. 2012

J. Polym. Sci. A Polym. Chem.

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We describe a versatile approach to synthesize glycosylated polyphosphazenes with controllable density of glycosyl groups. These glycopolymers have been synthesized by the nucleophilic substitution of poly(dichlorophosphazene) with propargylamine and subsequent “thiol–yne” click reaction between poly[di(propargylamine)phosphazene] and 2,3,4,6‐tetra‐O‐acetyl‐1‐thio‐β‐D‐glucopyranose (SH‐GlcAc4). The polymers were characterized with FTIR and 1H NMR. We found that the high steric hindrance of SH‐GlcAc4 plays a key role in the overall reaction process, and ∼55% of the alkyne groups participate in the “thiol–yne” click reaction. About 8% of the alkyne groups convert to alkene groups at the end of click reaction. The substitution of alkyne/alkane mixture was conducted to reduce the alkyne density in the side groups of polyphosphazenes and minimize the influences of this steric effect. Mixed‐substituent polyphosphazene was synthesized with 2:3 ratio of alkyne and alkane. In this case, almost no alkyne group remains after the “thiol–yne” click reaction, and thus the glycosylated polyphosphazene is able to form into micelles through self‐assembly process. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

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Section: Resultssupporting

confidence: 50%

Controllable glycosylation of polyphosphazene via radical thiol–yne click chemistry

Ren

Huang

et al. 2012

J. Polym. Sci. A Polym. Chem.

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“…(Fairbanks et al 2010) Since then, the thiol-yne reaction, along with the thiol-ene reaction, has been investigated for glycan coupling, and biomolecular functionalization of diverse materials. (Gupta et al 2010; Lo Conte et al 2010; Semsarilar et al 2010; Wang et al 2011; Wendeln et al 2010)…”

Section: Introductionmentioning

confidence: 99%

Photogenerated lectin sensors produced by thiol-ene/yne photo-click chemistry in aqueous solution

Norberg

Lee

Aastrup

et al. 2012

Biosensors and Bioelectronics

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The photoinitiated radical reactions between thiols and alkenes/alkynes (thiol-ene and thiol-yne chemistry) have been applied to a functionalization methodology to produce carbohydrate-presenting surfaces for analyses of biomolecular interactions. Polymer-coated quartz surfaces were functionalized with alkenes or alkynes in a straightforward photochemical procedure utilizing perfluorophenylazide (PFPA) chemistry. The alkene/alkyne surfaces were subsequently allowed to react with carbohydrate thiols in water under UV-irradiation. The reaction can be carried out in a drop of water directly on the surface without photoinitiator and any disulfide side products were easily washed away after the functionalization process. The resulting carbohydrate-presenting surfaces were evaluated in real-time studies of protein-carbohydrate interactions using a quartz crystal microbalance flow-through system with recurring injections of selected lectins with intermediate regeneration steps using low pH buffer. The resulting methodology proved fast, efficient and scalable to high-throughput analysis formats, and the produced surfaces showed significant protein binding with expected selectivities of the lectins used in the study.

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“…However there is little, if any, precedent for this in the literature at large. There is some evidence in favor of UVA-dependent thiol-yne covalent coupling of alkyne-tagged compounds with thiol-bearing cysteine residues [31, 32], however there are no readily available reports for an equivalent UVA-dependent direct coupling of alkyne functional groups with DNA. It is worth noting that, despite the requirement for UVA in the induction of 8-POP-DNA ICLs, the alkyne handle remains amenable to conjugation with an azide-tagged fluorescent reporter (Figures 3, 5 and 6), indicating that the alkyne functional group remained intact.…”

Section: Discussionmentioning

confidence: 99%

A clickable psoralen to directly quantify DNA interstrand crosslinking and repair

Evison

Actis

Fujii

2016

Bioorganic & Medicinal Chemistry

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DNA interstrand crosslinks (ICLs) represent physical obstacles to advancing replication forks and transcription complexes. A range of ICL-inducing agents have successfully been incorporated into cancer therapeutics. While studies have adopted UVA-activated psoralens as model ICL-inducing agents for investigating ICL repair, direct detection of the lesion has often been tempered by tagging the psoralen scaffold with a relatively large reporter group that may perturb the biological activity of the parent psoralen. Here a minimally-modified psoralen probe was prepared featuring a small alkyne handle suitable for click chemistry. The psoralen probe, designated 8-propargyloxypsoralen (8-POP), can be activated by UVA in vitro to generate ICLs that are susceptible to post-labeling with an azide-tagged fluorescent reporter via a copper-catalyzed reaction. A modified alkaline comet assay demonstrated that UVA-activated 8-POP proficiently generated ICLs in cells. Cellular 8-POP-DNA lesions were amenable to click-mediated ligation to fluorescent reporters in situ, which permitted their detection and quantitation by fluorescence microscopy and flow cytometry. Small molecule DNA repair inhibitors to 8-POP-treated cells attenuated the removal of 8-POP-DNA lesions, validating 8-POP as an appropriate probe for investigating cellular ICL repair. The post-labeling strategy applied in this study is inexpensive, rapid and highly modular in nature with the potential for multiple applications in DNA repair studies.

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Photoinduced Addition of Glycosyl Thiols to Alkynyl Peptides: Use of Free-Radical Thiol−Yne Coupling for Post-Translational Double-Glycosylation of Peptides

Cited by 90 publications

References 42 publications

Controllable glycosylation of polyphosphazene via radical thiol–yne click chemistry

Controllable glycosylation of polyphosphazene via radical thiol–yne click chemistry

Photogenerated lectin sensors produced by thiol-ene/yne photo-click chemistry in aqueous solution

A clickable psoralen to directly quantify DNA interstrand crosslinking and repair

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