Plasmon-triggered living photopolymerization for elaboration of hybrid polymer/metal nanoparticles

Kameche, Farid; Heni, Wajdi; Telitel, Siham; Ge, Dandan; Vidal, Loı̈c; Dumur, Frédéric; Gigmès, Didier; Lalevée, Jacques; Marguet, Sylvie; Douillard, Ludovic; Fiorini–Debuisschert, Céline; Bachelot, Renaud; Soppera, Olivier

doi:10.1016/j.mattod.2020.03.023

Cited by 23 publications

(36 citation statements)

References 59 publications

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“…Mono-crystalline Au nanocubes (fig. 7) were prepared by colloidal chemistry in aqueous solution, according to an already published protocol 15,35 , in presence of cetyltrimethylammonium bromide (CTAB) as the capping agent. Crystal growth is achieved by chemical reduction of Au+ ions on the surface of a gold seed (a small sphere with an initial size of 2 to 3 nm in diameter), resulting in the formation of a cubic shape 36 .…”

Section: Synthesis Of Au Nanocubesmentioning

confidence: 99%

Small-Angle X-ray Scattering: Characterization of cubic Au nanoparticles using Debye's scattering formula

Deumer¹,

Pauw²,

Marguet³

et al. 2021

Preprint

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We propose a versatile, user-friendly approach, named (Computing Debye's scattering formula for Extraordinary Formfactors) (CDEF), to approximately calculate scattering profiles of arbitrarily shaped nanoparticles for small-angle X-ray scattering (SAXS) using Debye's scattering formula, also known as the Debye equation. This equation generally allows to compute the scattering pattern of an ensemble of scatterers with a known form factor in the kinematic limit. The ensemble can hereby consist of atoms, atomic nuclei or larger shapes. In the method proposed in this paper, a quasi-randomly distributed point cloud in the desired particle shape is generated. Then, Debye's formula is applied to this ensemble of point scatterers to calculate the SAXS pattern of a single particle with random orientation. The quasi-random distribution ensures faster convergence compared to a true random distribution of scatterers, especially in the higher region of the momentum transfer q. In order to compute realistic SAXS curves of polydisperse nanoparticle ensembles with a given size distribution, the single particle master curve is rescaled and convolved with the size distribution. This allows us to fit measured data in reasonable time.We have used the method to evaluate scattering data of Au nanocubes with truncated or rounded edges, which were measured at the four-crystal monochromator beamline of PTB at the synchrotron radiation facility BESSY II in Berlin. Our implementation of this method is fast enough to run on a single desktop computer and perform model fits within minutes. The accuracy of the method was analyzed by comparison with analytically known form factors and another implementation, the SPONGE, based on a similiar principle but with fewer assumptions. Additionally, the SPONGE coupled to McSAS3 allows us to further retrieve information on the uncertainty of the size distribution using a Monte-Carlo uncertainty estimation algorithm.

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Section: Synthesis Of Au Nanocubesmentioning

confidence: 99%

Small-Angle X-ray Scattering: Characterization of cubic Au nanoparticles using Debye's scattering formula

Deumer¹,

Pauw²,

Marguet³

et al. 2021

Preprint

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“…[7] Optical near-field photopolymerization attracted recently much interest, as a smart approach to obtain hybrid NPs with a control at the nanoscale. [8,9] The idea is to trigger radical photopolymerization reactions on the surface of metallic NPs by using two essential features of the optical near-field: i): the exaltation of the incident electromagnetic field by localized plasmon resonance phenomena, ii): the spatial localization of the exalted electromagnetic field at the vicinity of the metallic NPs.…”

Section: Introductionmentioning

confidence: 99%

“…Both photopolymers are generated through a free radical photopolymerization process whose mechanism is described elsewhere. [8,9] These two configurations were chosen not only to…”

Section: Introductionmentioning

confidence: 99%

Plasmonic Au Nanoparticle Arrays for Monitoring Photopolymerization at the Nanoscale

Khitous

Lin

Kameche

et al. 2021

ACS Appl. Nano Mater.

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The localized surface plasmon resonance (LSPR) of Au nanoparticles (NPs) was used to monitor photopolymerization at the nanoscale, by in situ monitoring the optical response of AuNPs during the light-induced polymerization process. To show the interest of this approach, two configurations were used which correspond to a resonant and a non-resonant excitation regime between the photopolymer and the AuNPs used as nanoprobes. We show that not only this method enables the progress monitoring of the photopolymerization reaction at the nanometric scale but also can highlight the near-field coupling effect responsible for the acceleration of the photoinduced reaction. This methodology appears very interesting to study the photoinduced nanofabrication processes of metal/polymer hybrid nanoparticles and more globally as a methodology to study the photopolymerization reactions at the nanometric scale.

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“…In this context, the first example of nanoscale polymer functionalization using a controlled polymerization reaction has very recently been reported by Soppera and coworkers demonstrating re‐initiation using near‐field mode induced ATRP, and by this, showing preparation of multifunctional metal/polymer nanostructures. [ 36 ] Compared to ATRP, iniferter initiated polymerization is versatile as it offers polymerization control without requiring additional radical sources such as AIBN. [ 25b,37 ] This is especially useful for functionalization of nanoscale pores with restricted pore accessibility.…”

Section: Introductionmentioning

confidence: 99%

Surface Plasmons and Visible Light Iniferter Initiated Polymerization for Nanolocal Functionalization of Mesoporous Separation Layers

John

Stanzel

Andrieu‐Brunsen

2021

Adv Funct Materials

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Although the technological relevance of mesoporous ceramic polymer hybrid materials is well accepted, missing functionalization concepts enabling 3D nanoscale local control of polymer placement into mesoporous materials, including thin films, and ideally using controlled polymerization techniques limit the application potential. Here, nanolocal functionalization of mesoporous separation layers using controlled, visible light iniferter initiated polymerization allowing responsive polymer functionalization locally limited to the irradiated spot is introduced. Thereby, two visible light sensitive iniferters, s-p-trimethoxysilylbenzyl-S´-dodecyltrithiocarbonate and 4-cyano-4-((dodecylsulfanylthiocarbonyl)sulfanyl)pentanoic acid, are developed for polymer functionalization of mesoporous films in a grafting from and a grafting through approach. 3D nanolocal polymer placement close to the proximity of the plasmonic field source is demonstrated by combining these visible light iniferter initiated polymerizations with optical near field modes, such as localized surface plasmon resonance (LSPR). As the location of the LSPR in mesoporous films can be controlled by placing metal alloy nanoparticles into these films and film thicknesses can be adjusted, this strategy is applied for precise positioning of polymers into mesoporous films with nanolocal control in three dimensions and thus reduces the gap in precision of functional group positioning between technological and biological nanopores.

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Plasmon-triggered living photopolymerization for elaboration of hybrid polymer/metal nanoparticles

Cited by 23 publications

References 59 publications

Small-Angle X-ray Scattering: Characterization of cubic Au nanoparticles using Debye's scattering formula

Small-Angle X-ray Scattering: Characterization of cubic Au nanoparticles using Debye's scattering formula

Plasmonic Au Nanoparticle Arrays for Monitoring Photopolymerization at the Nanoscale

Surface Plasmons and Visible Light Iniferter Initiated Polymerization for Nanolocal Functionalization of Mesoporous Separation Layers

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