Click-based thiol-ene photografting of COOH groups to SiO2 nanoparticles: Strategies comparison

Penelas, María Jazmín; Soler-Illia, Galo J.A.A.; Levi, Valeria; Bordoni, Andrea; Wolosiuk, Alejandro

doi:10.1016/j.colsurfa.2018.11.023

Cited by 9 publications

(12 citation statements)

References 50 publications

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“…Scheme presents a simplified description of the PNIPAm grafting on SiO 2 NPs. In the first step, SiO 2 NPs were surface functionalized by a “one-pot” reaction, with the addition of vinyltriethoxysilane (VTES) directly into the alcosol of the Stöber synthesis, resulting in vinyl modified NPs, SiO 2 -V NPs. , In the second step, the previously immobilized vinyl groups worked as coupling agents to introduce reactive groups onto the particle surface and the PNIPAm was then grafted-on using these groups. This synthesis methodology allowed us to obtain core-brush SiO 2 NPs covered with PNIPAm brushes of controlled thickness.…”

Section: Resultsmentioning

confidence: 99%

Light-Induced Polymer Response through Thermoplasmonics Transduction in Highly Monodisperse Core-Shell-Brush Nanosystems

et al. 2020

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Smart nanosystems that transduce external stimuli to physical changes are an inspiring challenge in current materials chemistry. Hybrid organic−inorganic materials attract great attention due to the combination of building blocks responsive to specific external solicitations. In this work, we present a sequential method for obtaining an integrated core-shell-brush nanosystem that transduces light irradiation into a particle size change through a thermoplasmonic effect. We first synthesize hybrid monodisperse systems made up of functionalized silica colloids covered with controllable thermoresponsive poly(Nisopropylacrylamide), PNIPAm, brushes, produced through radical photopolymerization. This methodology was successfully transferred to Au@SiO 2 nanoparticles, leading to a core-shell-brush architecture, in which the Au core acts as a nanosource of heat; the silica layer, in turn, adapts the metal and polymer interfacial chemistries and can also host a fluorescent dye for bioimaging. Upon green LED irradiation, a light-to-heat conversion process leads to the shrinkage of the external polymer layer, as proven by in situ DLS. Our results demonstrate that modular hybrid nanosystems can be designed and produced with photothermo-physical transduction. These remote-controlled nanosystems present prospective applications in smart carriers, responsive bioscaffolds, or soft robotics.

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Section: Resultsmentioning

confidence: 99%

Light-Induced Polymer Response through Thermoplasmonics Transduction in Highly Monodisperse Core-Shell-Brush Nanosystems

et al. 2020

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“…In the first step, SiO2 NPs were surface functionalized by a "one-pot" reaction, adding an organic silane agent, vinyltriethoxysilane (VTES), directly into the alcosol of the Stöber synthesis, resulting in vinyl modified NPs, SiO2-V NPs. 57,58 In the second step, the previously immobilized vinyl groups worked as a copolymerizable site for the PNIPAm grafting. This synthesis methodology allowed obtaining core-brush SiO2 NPs covered with PNIPAm brushes of controlled thickness.…”

Section: Optimization Of Pnipam Photografting On Sio2 Nps Surfacementioning

confidence: 99%

A light-remote-controllable Core-Shell-Brush nanosystem prepared through a sequential one-pot strategy

Penelas¹,

Contreras

Angelomé³

et al. 2019

Preprint

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The development of smart nanosystems that transduce external stimuli to physical changes is an inspiring challenge in current materials chemistry. In this framework, hybrid organic-inorganic nanosystems attract great attention due to the combination of building blocks that respond to specific external stimuli. Poly(N-isopropylacrylamide) –PNIPAm- has been explored in temperature-responsive actuators with applications in drug or gene delivery, biocatalysis, or separation. However, little work has been dedicated to produce nanosystems that couple thermal actuation with other external stimuli that can remote-control the mechanical response. In this work, we present a sequential method for obtaining core-shell-brush nanosystems that can transduce light irradiation into a mechanical response through a thermoplasmonic effect. We synthetize hybrid monodisperse silica colloids covered with controllable PNIPAm brushes, produced through a simple and reproducible radical photopolymerization. This methodology can be applied successfully to Au@SiO2 nanoparticles, leading to a core-shell-brush architecture. When these systems are irradiated with green LED light, direct light-to-heat conversion leads to shrinkage of the polymer layer. Our results demonstrate that modular hybrid nanosystems composed of a plasmonic heating module, a buffer silica layer, and an external thermo-responsive brush can be designed and produced with photo-thermo-mechanical transduction, which can be applied in smart carriers or soft robotics.

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“…A common strategy to add functional groups to SiO x -coated NPs is to first hydrolyze silane-based reagents to form terminal silanol groups (Si–OH) on these reagents, followed by their condensation with the silanol groups on the surfaces of the SiO x coating. − An advantage of using silane-based reagents for such surface modifications is their ability to rapidly form covalent silyl ether (M–O–Si–R) bonds between the reagent and the surfaces (M = Si or a metal atom) of the NPs at relatively low temperatures. − Silane-based reagents can, however, have several limitations that include extensive procedures required to control the reaction conditions, to control the moisture content, and to minimize side reactions (e.g., self-condensation to form siloxanes). − Another disadvantage of using silanes as molecular reagents is the relatively limited number of functional groups available for a direct or one-step attachment to silanol groups on the SiO x -coated NPs. For example, relatively few studies use silane-based reagents to functionalize NPs with −COOH-terminated surfaces since multi-step processes are required to create these surface functional groups. − …”

Section: Introductionmentioning

confidence: 99%

Tuning the Surface Chemistry of Second-Harmonic-Active Lithium Niobate Nanoprobes Using a Silanol–Alcohol Condensation Reaction

et al. 2021

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The surface functionalization of nanoparticles (NPs) is of great interest for improving the use of NPs in, for example, therapeutic and diagnostic applications. The conjugation of specific molecules with NPs through the formation of covalent linkages is often sought to provide a high degree of colloidal stability and biocompatibility, as well as to provide functional groups for further surface modification. NPs of lithium niobate (LiNbO3) have been explored for use in second–harmonic-generation (SHG)-based bioimaging, expanding the applications of SHG-based microscopy techniques. The efficient use of SHG-active LiNbO3 NPs as probes will, however, require the functionalization of their surfaces with molecular reagents such as polyethylene glycol and fluorescent molecules to enhance their colloidal and chemical stability and to enable a correlative imaging platform. Herein, we demonstrate the surface functionalization of LiNbO3 NPs through the covalent attachment of alcohol-based reagents through a silanol–alcohol condensation reaction. Alcohol-based reagents are widely available and can have a range of terminal functional groups such as carboxylic acids, amines, and aldehydes. Attaching these molecules to NPs through the silanol–alcohol condensation reaction could diversify the reagents available to modify NPs, but this reaction pathway must first be established as a viable route to modifying NPs. This study focuses on the attachment of a linear alcohol functionalized with carboxylic acid and its use as a reactive group to further tune the surface chemistry of LiNbO3 NPs. These carboxylic acid groups were reacted to covalently attach other molecules to the NPs using copper-free click chemistry. This derivatization of the NPs provided a means to covalently attach polyethylene glycols and fluorescent probes to the NPs, reducing NP aggregation and enabling multimodal tracking of SHG nanoprobes, respectively. This extension of the silanol–alcohol condensation reaction to functionalize the surfaces of LiNbO3 NPs can be extended to other types of nanoprobes for use in bioimaging, biosensing, and photodynamic therapies.

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Click-based thiol-ene photografting of COOH groups to SiO2 nanoparticles: Strategies comparison

Cited by 9 publications

References 50 publications

Light-Induced Polymer Response through Thermoplasmonics Transduction in Highly Monodisperse Core-Shell-Brush Nanosystems

Light-Induced Polymer Response through Thermoplasmonics Transduction in Highly Monodisperse Core-Shell-Brush Nanosystems

A light-remote-controllable Core-Shell-Brush nanosystem prepared through a sequential one-pot strategy

Tuning the Surface Chemistry of Second-Harmonic-Active Lithium Niobate Nanoprobes Using a Silanol–Alcohol Condensation Reaction

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