Reversible trapping and reaction acceleration within dynamically self-assembling nanoflasks

Zhao, Hui; Sen, Shamik; Udayabhaskararao, Thumu; Sawczyk, Michał; Kučanda, Kristina; Manna, Debasish; Kundu, Pintu K.; Lee, Jiwoong; Král, Petr; Klajn, Rafał

doi:10.1038/nnano.2015.256

Cited by 333 publications

(313 citation statements)

References 49 publications

Supporting

Mentioning

312

Contrasting

Order By: Relevance

“…Only now, however, are organized assemblies of metal nanoparticles beginning to serve in a similar capacity as hosts for molecular guests. In organic solvents, for example, light-induced dipoledipole interactions between gold nanoparticles with azobenzenefunctionalized thiolate ligands were recently used to entrap and catalyse the reactions of polar and alkylaromatic substrates 8 . By design, substrates were entrapped during nanoparticle aggregation to overcome the poor uptake and diffusion of molecular guests into colloidal nanocrystal assemblies.…”

mentioning

confidence: 99%

Host–guest chemistry with water-soluble gold nanoparticle supraspheres

et al. 2016

View full text Add to dashboard Cite

The uptake of molecular guests, a hallmark of the supramolecular chemistry of cages and containers, has yet to be documented for soluble assemblies of metal nanoparticles. Here we demonstrate that gold nanoparticle-based supraspheres serve as a host for the hydrophobic uptake, transport and subsequent release of over two million organic guests, exceeding by five orders of magnitude the capacities of individual supramolecular cages or containers and rivalling those of zeolites and metal-organic frameworks on a mass-per-volume basis. The supraspheres are prepared in water by adding hexanethiol to polyoxometalate-protected 4 nm gold nanoparticles. Each 200 nm assembly contains hydrophobic cavities between the estimated 27,400 gold building blocks that are connected to one another by nanometre-sized pores. This gives a percolated network that effectively absorbs large numbers of molecules from water, including 600,000, 2,100,000 and 2,600,000 molecules (35, 190 and 234 g l ) of para-dichorobenzene, bisphenol A and trinitrotoluene, respectively.H ost-guest phenomena that involve the uptake of gases and small molecules are associated with the supramolecular chemistry of soluble capsules, cages and containers [1][2][3][4][5] or, alternatively, with heterogeneous reactions of porous solid-state materials such as zeolites 6 and metal-organic frameworks 7 . Only now, however, are organized assemblies of metal nanoparticles beginning to serve in a similar capacity as hosts for molecular guests. In organic solvents, for example, light-induced dipoledipole interactions between gold nanoparticles with azobenzenefunctionalized thiolate ligands were recently used to entrap and catalyse the reactions of polar and alkylaromatic substrates 8 . By design, substrates were entrapped during nanoparticle aggregation to overcome the poor uptake and diffusion of molecular guests into colloidal nanocrystal assemblies. However, the uptake of molecular guests, a trait of supramolecular and solid-state chemistry, has so far not been achieved for colloidal nanoparticle assemblies.For that to occur, a thermodynamically favourable driving force must be combined with a porous structure whose interior architecture features host cavities, along with pathways for the effective diffusion of molecular guests from the exterior (bulk solution) to host domains deeply buried in the assembly's interior. If this were achieved, colloidal metal-nanoparticle assemblies could emerge as a new class of functional nano-engineered structures that are uniquely positioned between supramolecular containers and porous solid-state materials.We report a new class of functional assemblies, wherein the hydrophobic effect 9,10 drives the spontaneous uptake of alkyl and alkylaromatic guests 11 by porous 200 nm diameter supraspheres whose host capacities are orders of magnitude larger than those of individual cages or containers. On a mass-per-volume basis, the level of uptake rivals those of zeolites and metal-organic frameworks, which, for methane at elevated pressures, r...

show abstract

mentioning

confidence: 99%

Host–guest chemistry with water-soluble gold nanoparticle supraspheres

et al. 2016

View full text Add to dashboard Cite

show abstract

“…1 top row, left panel). 118 The nano-flasks can be reversibly self-assembled and disassembled upon UV and visible light irradiation, allowing the encapsulated molecules within the nano-flasks to be trapped and released dynamically. The selectivity of molecules encapsulated in the nano-flasks can be optimised by functionalising the NPs with ligands of different functional groups and multi-wall layers.…”

Section: Hybrid Nanomachinesmentioning

confidence: 99%

Artificial molecular and nanostructures for advanced nanomachinery

et al. 2018

View full text Add to dashboard Cite

show abstract

“…Gold nanoparticles (AuNPs)—due to chemical robustness, easy preparation and functionalization—are often used as a model system for studying nanoscale phenomena (Daniel and Astruc 2004; Hakkinen 2012; Kalsin et al 2006; Nealon et al 2012; Sashuk 2012; Sashuk et al 2012, 2013; Teulle et al 2015; Wells et al 2015; Zhao et al 2016). Moreover, the pristine chemical and physical properties of nanoscopic gold provide additional appeal for applications such as catalysis or sensing (Giljohann et al 2010; Jans and Huo 2012; Kale et al 2014; Mikami et al 2013; Saha et al 2012; Stratakis and Garcia 2012; Yeh et al 2012).…”

Section: Introductionmentioning

confidence: 99%

A halogen-free synthesis of gold nanoparticles using gold(III) oxide

Sashuk

Rogaczewski

2016

J Nanopart Res

View full text Add to dashboard Cite

Gold nanoparticles are one of the most used nanomaterials. They are usually synthesized by the reduction of gold(III) chloride. However, the presence of halide ions in the reaction mixture is not always welcome. In some cases, these ions have detrimental influence on the morphology and structure of resulting nanoparticles. Here, we present a simple and halogen-free procedure to prepare gold nanoparticles by reduction of gold(III) oxide in neat oleylamine. The method provides the particles with an average size below 10 nm and dispersity of tens of percent. The process of nanoparticle formation was monitored using UV–Vis spectroscopy. The structure and chemical composition of the nanoparticles was determined by SEM, XPS and EDX. We also proposed the mechanism of reduction of gold(III) oxide based on MS, IR and NMR data. Importantly, the synthetic protocol is general and applicable for the preparation of other coinage metal nanoparticles from the corresponding metal oxides. For instance, we demonstrated that the absence of halogen enables efficient alloying of metals when preparing gold–silver bimetallic nanoparticles.Electronic supplementary materialThe online version of this article (doi:10.1007/s11051-016-3576-x) contains supplementary material, which is available to authorized users.

show abstract

Reversible trapping and reaction acceleration within dynamically self-assembling nanoflasks

Cited by 333 publications

References 49 publications

Host–guest chemistry with water-soluble gold nanoparticle supraspheres

Host–guest chemistry with water-soluble gold nanoparticle supraspheres

Artificial molecular and nanostructures for advanced nanomachinery

A halogen-free synthesis of gold nanoparticles using gold(III) oxide

Contact Info

Product

Resources

About