Impact of the Solvent Quality on the Local Dynamics of Soft and Swollen Polymer Nanoparticles Functionalized with Polymer Chains

Kim, Young-Gon; Thérien-Aubin, Héloı̈se

doi:10.1021/acs.macromol.0c00346

Cited by 6 publications

(4 citation statements)

References 69 publications

(99 reference statements)

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“…In the past, the effect of water on the physical properties of NOHM-based mixtures has been explored. , It has recently been shown that the chemical and physical properties of solvents can have a significant impact on the behavior, conformation, and dynamics of nanoparticle-tethered ligands/polymers . However, there is currently a lack of understanding of how the hydrogen bonding nature, polarity, and size of the secondary fluid molecule affect relevant transport properties of ionically bound polymers in solution.…”

Section: Introductionmentioning

confidence: 99%

Dynamic Mixing Behaviors of Ionically Tethered Polymer Canopy of Nanoscale Hybrid Materials in Fluids of Varying Physical and Chemical Properties

et al. 2021

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An emerging area of sustainable energy and environmental research is focused on the development of novel electrolytes that can increase the solubility of target species and improve subsequent reaction performance. Electrolytes with chemical and structural tunability have allowed for significant advancements in flow batteries and CO2 conversion integrated with CO2 capture. Liquid-like nanoparticle organic hybrid materials (NOHMs) are nanoscale fluids that are composed of inorganic nanocores and an ionically tethered polymeric canopy. NOHMs have been shown to exhibit enhanced conductivity making them promising for electrolyte applications, though they are often challenged by high viscosity in the neat state. In this study, a series of binary mixtures of NOHM-I-HPE with five different secondary fluids, water, chloroform, toluene, acetonitrile, and ethyl acetate, were prepared to reduce the fluid viscosity and investigate the effects of secondary fluid properties (e.g., hydrogen bonding ability, polarity, and molar volume) on their transport behaviors, including viscosity and diffusivity. Our results revealed that the molecular ratio of secondary fluid to the ether groups of Jeffamine M2070 (λSF) was able to describe the effect that secondary fluid has on transport properties. Our findings also suggest that in solution, the Jeffamine M2070 molecules exist in different nanoscale environments, where some are more strongly associated with the nanoparticle surface than others, and the conformation of the polymer canopy was dependent on the secondary fluid. This understanding of the polymer conformation in NOHMs can allow for the better design of an electrolyte capable of capturing and releasing small gaseous or ionic species.

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Section: Introductionmentioning

confidence: 99%

Dynamic Mixing Behaviors of Ionically Tethered Polymer Canopy of Nanoscale Hybrid Materials in Fluids of Varying Physical and Chemical Properties

et al. 2021

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“…However, controlling the aggregation state of NP in the solvent system is crucial for the formation of deposited structures after completely drying, which can be achieved through the solvent solubility. − The phenomenon is particularly important for the polymer-grafted NP (also known as hair NP [HNP]). − At low grafting densities, the configuration of long-chain polymer brushes grafted on the surface of NP transforms between collapse and stretching (swelling) due to changes in the solubility of the solvent components. − This conformational transition affects the interactions between the HNP and solvents, thus promoting effective dispersion/aggregation. The stimulus responsiveness of HNP makes it possible to generate complex surface structures by colloidal deposition methods. − One powerful technique for preparing HNP with grafting brushes capable of conformational transitions is surface-initiated atom-transfer radical polymerization (SI-ATRP), which offers precise control over the molecular weight and architecture of tethered polymers by growing polymer chains from immobilized initiators on the particle surface.…”

Section: Introductionmentioning

confidence: 99%

Azeotropic Binary Solvent System Containing Nonfluorinated Polymer-Grafted Silica Nanoparticles for the Fabrication of a Superhydrophobic Surface

et al. 2023

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This study describes a method for fabricating a superhydrophobic surface on glass via a colloidal deposition technique based on solvent evaporation-induced aggregation. Silica nanoparticles with a low grafting density of long-chain poly-(cyclohexyl methacrylate) (PCH) were dispersed in a binary solvent system consisting of tetrahydrofuran (THF) and methanol (MeOH) with an azeotropic point and the nonfluorinated and hydrophobic PCHMA having a solubility parameter similar to that of THF. In the early stages of evaporation, the binary mixtures tend to induce the aggregation of PCH-NP due to the azeotropic point of the solvent components, leading to the formation of surface structures ranging from smooth to rough on the substrate. By adjusting the initial ratio of the binary solvents, a superhydrophobic coating with a water contact angle of 154 ± 2°and a sliding angle of less than 10°was achieved at a THF content of 60 wt %. This facile approach using azeotropes successfully shows that changes in the solvent composition of the binary solvent system during evaporation can be used to prepare superhydrophobic coatings with well-controlled surface structures.

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“…Polymer dissolution, a phenomenon driven by solvent diffusion and polymer chain disentanglement, induces full or partial miscibility of the polymer in a suitable solvent. − Interaction with solvent molecules causes the polymer chains to swell, and a subsequent evaporation of the solvent typically leaves behind a roughened surface. Harnessing these fundamental insights, we have developed a versatile technique to generate uniform and spatially defined rough patches on the surfaces of non-cross-linked, smooth polystyrene (PS) microspheres.…”

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confidence: 99%

Selective Vapor Condensation for the Synthesis and Assembly of Spherical Colloids with a Precise Rough Patch

Guillot,

Brahana,

Al Harraq

et al. 2024

JACS Au

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Patchy particles occupy an increasingly important space in soft matter research due to their ability to assemble into intricate phases and states. Being able to fine-tune the interactions among these particles is essential to understanding the principles governing the self-assembly processes. However, current fabrication techniques often yield patches that deviate chemically and physically from the native particles, impeding the identification of the driving forces behind self-assembly. To overcome this challenge, we propose a new approach to synthesizing spherical colloids with a well-defined rough patch on their surface. By treating polystyrene microspheres with vapors of a good solvent, here an acetone−water mixture, we achieve selective polymer corrugation on the particle surface resulting in a chemically similar yet rough surface patch. The key step is the selective condensation of the acetone−water vapors on the apex of the polystyrene microparticles immobilized on a substrate, which leads to rough patch formation. We leverage the ability to tune the vapor−liquid equilibrium of the volatile acetone−water mixture to precisely control the polymer corrugation on the particle surface. We demonstrate the dependence of patch formation on particle and substrate wettability, with the condensation occurring on the particle apex only when it is more wettable than the substrate, which is consistent with Volmer's classical nucleation theory. By combining experiments and molecular dynamics simulations, we identify the role of the rough patch in the depletion interactiondriven self-assembly of the microspheres, which is crucial for designing programmable supracolloidal structures.

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Impact of the Solvent Quality on the Local Dynamics of Soft and Swollen Polymer Nanoparticles Functionalized with Polymer Chains

Cited by 6 publications

References 69 publications

Dynamic Mixing Behaviors of Ionically Tethered Polymer Canopy of Nanoscale Hybrid Materials in Fluids of Varying Physical and Chemical Properties

Dynamic Mixing Behaviors of Ionically Tethered Polymer Canopy of Nanoscale Hybrid Materials in Fluids of Varying Physical and Chemical Properties

Azeotropic Binary Solvent System Containing Nonfluorinated Polymer-Grafted Silica Nanoparticles for the Fabrication of a Superhydrophobic Surface

Selective Vapor Condensation for the Synthesis and Assembly of Spherical Colloids with a Precise Rough Patch

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