Versatile strained alkyne modified water-soluble AuNPs for interfacial strain promoted azide–alkyne cycloaddition (I-SPAAC)

Gobbo, Pierangelo; Mossman, Zack; Nazemi, Ali; Niaux, Aurelia; Biesinger, Mark C.; Gillies, Elizabeth R.; Workentin, Mark S.

doi:10.1039/c3tb21799j

Cited by 33 publications

(47 citation statements)

References 43 publications

(51 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Nevertheless, interfacial unmasking of DIBO‐AuNPs was fast (<10 min) in reasonably dilute solutions of AuNPs (0.25 mg mL −1 solvent) and led to a clean and quantitative yield of the strained alkyne derivatized AuNP product, which contained 0.136 μmol interfacial DIBO per mg of AuNP. This is double that of ADIBO used in the previous system shown in Scheme , thus allowing for greater capitalization on the high load capacity of AuNPs . Additionally, the only by‐product generated (CO) is released as a gas, which avoids any impurities and the need for further purification of DIBO‐AuNPs.…”

Section: Resultsmentioning

confidence: 98%

“…The derivative of the TGA curve showed that there are two ligands that decompose at distinctly different temperatures (Figure S4): a larger component at 265 °C and a small component at 375 °C. By comparing to the TGA data with that of the MeO‐EG 3 ‐AuNP starting material, the ligand decomposing at 265 °C was assigned to MeO‐EG 3 ‐S − , whereas the ligand at 375 °C was assigned to photoDIBO‐EG 4 ‐S − . From the combination of 1 H NMR data, deconvolution of the TGA derivative curve, and TEM analysis, and assuming that these AuNPs are spherical and monodispersed in size, it was possible to calculate an approximate molecular formula of photoDIBO‐AuNPs to be Au 800 (MeO‐EG 3 ‐S) 270 (photoDIBO‐EG 4 ‐S) 30 .…”

Section: Resultsmentioning

confidence: 99%

“…The Workentin group has made efforts to prepare water soluble AuNP templates that can undergo interfacial SPAAC (i‐SPAAC) reaction for the facile post‐synthetic modification of the gold core. Recently, we reported ADIBO‐derivatized water‐soluble AuNPs that were synthesized by a post‐synthetic interfacial amide coupling reaction between carboxy‐terminated AuNPs and an ADIBO‐amine (Scheme ) . Although these ADIBO‐modified AuNPs demonstrated efficient i‐SPAAC reactivity and water solubility, their synthesis requires an interfacial coupling reaction that did not proceed to completion.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

“Shine & Click” Photo‐Induced Interfacial Unmasking of Strained Alkynes on Small Water‐Soluble Gold Nanoparticles

Luo

Gobbo

McNitt

et al. 2016

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

In this study, we report the design, synthesis, and characterization of small 3 nm water soluble gold nanoparticles (AuNPs) that feature cyclopropenone-masked strained alkyne moieties capable of undergoing interfacial strain-promoted cycloaddition (i-SPAAC) with azides after exposure to UV-A light. A strained alkyne precursor was incorporated onto AuNPs by direct ligand exchange of a thiol-modified cyclopropenone-masked dibenzocyclooctyne (photoDIBO) ligand. These photoDIBO-AuNPs were characterized by H NMR, IR, and UV/Vis spectroscopy, as well as transmission electron microscopy (TEM) and thermogravimetric analysis (TGA), and the extent of modification was quantified. Upon irradiation with UV-A light, photoDIBO-AuNPs underwent efficient and quantitative regeneration of the parent strained alkyne by photochemical decarbonylation to afford DIBO-derivatized AuNPs. DIBO-AuNPs were found to react cleanly and rapidly (k=5.3×10 m s ) by an interfacial strain-promoted alkyne-azide cycloadditon (i-SPAAC) with benzyl azide, which served as a simple model system. Furthermore, DIBO-AuNPs were reacted with various azides and a nitrone (interfacial strain-promoted alkyne-nitrone cycloaddition, i-SPANC) to showcase the generality of this approach for the facile modification of AuNP surfaces and their properties. The cyclopropenone-based photo-triggered click chemistry at the interface of water-soluble AuNPs offers exciting opportunities for the atom-by-atom control and assembly of functional materials for applications in materials and biomaterials science as well as in chemical biology.

show abstract

Section: Resultsmentioning

confidence: 98%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

“Shine & Click” Photo‐Induced Interfacial Unmasking of Strained Alkynes on Small Water‐Soluble Gold Nanoparticles

Luo

Gobbo

McNitt

et al. 2016

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

show abstract

“…The [3 + 2] Huisgen cycloaddition and the copper catalyzed [3 + 2] Huisgen cycloaddition with dipolarophiles, the strained-promoted alkyne-azide cycloaddition (SPAAC) with strained alkynes and the Staudinger-Bertozzi ligation. 10,11 While the [3 + 2] Huisgen cycloaddition and its catalyzed version are not completely compatible with AuNPs chemistry because the high temperature or the Cu(I) required to push the reaction to completion cause severe nanoparticle aggregation, 12 the SPAAC reaction presents limited chemoselectivity due to the possibility of nucleophilic attacks (especially from thiols and amines largely present in biomolecules) to the highly reactive strained triple bond. [13][14][15] A recent work of ours highlighted this issue showing how post assembly deprotection of peptides once "clicked" on the AuNP surface was necessary to efficiently synthesize a nanoparticle bioconjugate through the SPAAC reaction.…”

mentioning

confidence: 99%

Small gold nanoparticles for interfacial Staudinger–Bertozzi ligation

et al. 2015

Self Cite

View full text Add to dashboard Cite

Small gold nanoparticles (AuNPs) that possess interfacial methyl-2-(diphenylphosphino)benzoate moieties have been successfully synthesized (Staudinger-AuNPs) and characterized by multi-nuclear MR spectroscopy, transmission electron microscopy (TEM), UV-Vis spectroscopy, thermogravimetric analysis, and X-ray photoelectron spectroscopy (XPS). In particular, XPS was remarkably sensitive for characterization of the novel nanomaterial, and in furnishing proof of its interfacial reactivity. These Staudinger-AuNPs were found to be stable to the oxidation of the phosphine center. The reaction with benzyl azide in a Staudinger-Bertozzi ligation, as a model system, was investigated using (31)P NMR spectroscopy. This demonstrated that the interfacial reaction was clean and quantitative. To showcase the potential utility of these Staudinger-AuNPs in bioorganic chemistry, a AuNP bioconjugate was prepared by reacting the Staudinger-AuNPs with a novel azide-labeled CRGDK peptide. The CRGDK peptide could be covalently attached to the AuNP efficiently, chemoselectively, and with a high loading.

show abstract

“…The attraction of the approach described here is that in a single step, AuNPs can be prepared having a strained alkyne at its surface for further modification under metal free conditions. [24] …”

Section: Resultsmentioning

confidence: 99%

Exploring Strain‐Promoted 1,3‐Dipolar Cycloadditions of End Functionalized Polymers

Ledin

Kolishetti

Hudlikar

et al. 2014

Chemistry A European J

View full text Add to dashboard Cite

Strain-promoted 1,3-dipolar cycloaddition of cyclooctynes with 1,3-dipoles such as azides, nitrones, and nitrile oxides, are of interest for the functionalization of polymers. In this study, we have explored the use of a 4-dibenzocyclooctynol (DIBO)-containing chain transfer agent in reversible addition–fragmentation chain transfer polymerizations. The controlled radical polymerization resulted in well-defined DIBO-terminating polymers that could be modified by 1,3-dipolar cycloadditions using nitrones, nitrile oxides, and azides having a hydrophilic moiety. The self-assembly properties of the resulting block copolymers have been examined. The versatility of the methodology was further demonstrated by the controlled preparation of gold nanoparticles coated with the DIBO-containing polymers to produce materials that can be further modified by strain-promoted cyclo-additions.

show abstract

Versatile strained alkyne modified water-soluble AuNPs for interfacial strain promoted azide–alkyne cycloaddition (I-SPAAC)

Abstract: Versatile water-soluble AuNPs that incorporate an interfacial strained alkyne were synthesized and their reactivity towards the I-SPAAC reaction was demonstrated by using azide-decorated polymersomes as bioorthogonal reaction partners.

Cited by 33 publications

References 43 publications

“Shine & Click” Photo‐Induced Interfacial Unmasking of Strained Alkynes on Small Water‐Soluble Gold Nanoparticles

“Shine & Click” Photo‐Induced Interfacial Unmasking of Strained Alkynes on Small Water‐Soluble Gold Nanoparticles

Small gold nanoparticles for interfacial Staudinger–Bertozzi ligation

Exploring Strain‐Promoted 1,3‐Dipolar Cycloadditions of End Functionalized Polymers

Contact Info

Product

Resources

About