Complete pH-Dependent Shape Recovery in Cubical Hydrogel Capsules after Large Osmotic Deformations

Kozlovskaya, Veronika; Xue, Bing; Dolmat, Maksim; Kharlampieva, Eugenia

doi:10.1021/acs.macromol.1c00650

Cited by 9 publications

(25 citation statements)

References 67 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…It is, however, less straightforward to determine the single nanogel compressibility and resistance to deformations. This can be achieved by directly imaging the nanogels , or performing scattering experiments at different osmotic pressures set by osmotic stress solutions or by performing AFM. , …”

Section: Softness and Characteristic Lengthsmentioning

confidence: 99%

How Softness Matters in Soft Nanogels and Nanogel Assemblies

et al. 2022

View full text Add to dashboard Cite

Softness plays a key role in determining the macroscopic properties of colloidal systems, from synthetic nanogels to biological macromolecules, from viruses to star polymers. However, we are missing a way to quantify what the term “softness” means in nanoscience. Having quantitative parameters is fundamental to compare different systems and understand what the consequences of softness on the macroscopic properties are. Here, we propose different quantities that can be measured using scattering methods and microscopy experiments. On the basis of these quantities, we review the recent literature on micro- and nanogels, i.e. cross-linked polymer networks swollen in water, a widely used model system for soft colloids. Applying our criteria, we address the question what makes a nanomaterial soft? We discuss and introduce general criteria to quantify the different definitions of softness for an individual compressible colloid. This is done in terms of the energetic cost associated with the deformation and the capability of the colloid to isotropically deswell. Then, concentrated solutions of soft colloids are considered. New definitions of softness and new parameters, which depend on the particle-to-particle interactions, are introduced in terms of faceting and interpenetration. The influence of the different synthetic routes on the softness of nanogels is discussed. Concentrated solutions of nanogels are considered and we review the recent results in the literature concerning the phase behavior and flow properties of nanogels both in three and two dimensions, in the light of the different parameters we defined. The aim of this review is to look at the results on micro- and nanogels in a more quantitative way that allow us to explain the reported properties in terms of differences in colloidal softness. Furthermore, this review can give researchers dealing with soft colloids quantitative methods to define unambiguously which softness matters in their compound.

show abstract

Section: Softness and Characteristic Lengthsmentioning

confidence: 99%

How Softness Matters in Soft Nanogels and Nanogel Assemblies

et al. 2022

View full text Add to dashboard Cite

show abstract

“…Conversely, a nonspherical shape of a hydrogel particle has been demonstrated to favor the particle passing through pores and channels with smaller-than-particle-size diameters . In our work on the multilayer hydrogel capsules, we have demonstrated that despite the inherent softness and high swelling of the capsule wall, the nonspherical multilayer hydrogel capsules with the shape of nonspherical template particles can be obtained after template dissolution. ,, …”

Section: Synthesis Of Two-dimensional and Three-dimensional Multilaye...mentioning

confidence: 77%

“…The cubical PMAA multilayer network capsules were synthesized as hydrogel replicas of cubic MnCO 3 microparticles (4 to 5 μm) through the chemical cross-linking of hydrogen-bonded multilayer films of PMAA and PVPON . Single-component (PMAA) 20 capsules with a 20-layer hydrogel wall were produced either by cross-linking PMAA layers with a bifunctional cross-linker or by using a PMAA-NH 2 copolymer assembled with PVPON, where PMAA-NH 2 layers were covalently bound through carbodiimide-assisted cross-linking, resulting in amide linkages between amino and carboxylic groups and followed by PVPON release at basic pH. , The two-component (PMAA-PVPON) 5 hydrogel capsules were obtained when PVPON-NH 2 was assembled with PMAA followed by the carbodiimide-assisted binding of PMAA to PVPON-NH 2 layers . Using discoid silicon microparticles with a large aspect ratio as sacrificial templates led to the discoidal hydrogel capsules, either single- or two-component, with the shape of a red blood cell, an erythrocyte …”

Section: Synthesis Of Two-dimensional and Three-dimensional Multilaye...mentioning

confidence: 99%

“…The deformation behavior of 5 μm cubical hydrogel microcapsules with a capsule wall made of a 10-layer (PMAA) hydrogel obtained via the templated assembly of PVPON and amine-containing PMAA copolymer (PMAA-NH 2 ) was studied in bulk solution at low and basic pH (Figure a–f). The cross-link density of at least 16 monomer units between two cross-links was necessary to obtain the hollow (PMAA) 10 capsules that could retain the cubical template shape after template dissolution (Figure g,h) . For osmotically induced deformation, the capsules were exposed to varying concentrations of a macromolecule, poly(styrenesulfonate sodium salt) (PSS; M w = 70 kDa), that could not permeate the capsule shell, and the capsule deformations in response to the osmotic pressure differences were observed using optical fluorescence microscopy.…”

Section: Mechanical Propertiesmentioning

confidence: 99%

Section: Mechanical Propertiesmentioning

confidence: 99%

See 2 more Smart Citations

Two-Dimensional and Three-Dimensional Ultrathin Multilayer Hydrogels through Layer-by-Layer Assembly

2022

Self Cite

View full text Add to dashboard Cite

Stimuli-responsive multilayer hydrogels have opened new opportunities to design hierarchically organized networks with properties controlled at the nanoscale. These multilayer materials integrate structural, morphological, and compositional versatility provided by alternating layer-by-layer polymer deposition with the capability for dramatic and reversible changes in volumes upon environmental triggers, a characteristic of chemically cross-linked responsive networks. Despite their intriguing potential, there has been limited knowledge about the structure–property relationships of multilayer hydrogels, partly because of the challenges in regulating network structural organization and the limited set of the instrumental pool to resolve structure and properties at nanometer spatial resolution. This Feature Article highlights our recent studies on advancing assembly technologies, fundamentals, and applications of multilayer hydrogels. The fundamental relationships among synthetic strategies, chemical compositions, and hydrogel architectures are discussed, and their impacts on stimuli-induced volume changes, morphology, and mechanical responses are presented. We present an overview of our studies on thin multilayer hydrogel coatings, focusing on controlling and quantifying the degree of layer intermixing, which are crucial issues in the design of hydrogels with predictable properties. We also uncover the behavior of stratified “multicompartment” hydrogels in response to changes in pH and temperature. We summarize the mechanical responses of free-standing multilayer hydrogels, including planar thin coatings and films with closed geometries such as hollow microcapsules and nonhollow hydrogel microparticles with spherical and nonspherical shapes. Finally, we will showcase potential applications of pH- and temperature-sensitive multilayer hydrogels in sensing and drug delivery. The knowledge about multilayer hydrogels can advance the rational design of polymer networks with predictable and well-tunable properties, contributing to modern polymer science and broadening hydrogel applications.

show abstract

Multilayer Hydrogel Microcubes: Effects of Templating Particle Morphology on Cubic Hydrogel Properties

Inman,

Kozlovskaya,

Nikishau

et al. 2023

Macro Materials & Eng

Self Cite

View full text Add to dashboard Cite

Non‐spherical stimuli‐responsive polymeric particles have shown critical importance in therapeutic delivery. Herein, pH‐responsive poly(methacrylic acid) (PMAA) cubic hydrogel microparticles are synthesized by crosslinking PMAA layers within PMAA/poly(N‐vinylpyrrolidone) hydrogen‐bonded multilayers templated on porous inorganic microparticles. This study investigates the effects of template porosity and surface morphology on the PMAA multilayer hydrogel microcube properties. It is found that the hydrogel structure depends on the template's calcination time and temperature. The pH‐triggered PMAA hydrogel cube swelling depends on the hydrogel's internal architecture, either hollow capsule‐like or non‐hollow continuous hydrogels. The loading efficiency of the doxorubicin (DOX) drug inside the microcubes is analyzed by high‐performance liquid chromatography (HPLC), and shows the dependenceof the drug uptake on the network structure and morphology controlled by the template porosity. Varying the template calcination from low (300 °C) to high (1000 °C) temperature results in a 2.5‐fold greater DOX encapsulation by the hydrogel cubes. The effects of hydrogel surface charge on the DOX loading and release are also studied using zeta‐potential measurements. This work provides insight into the effect of structural composition, network morphology, and pH‐induced swelling of the cubical hydrogels and may advance the development of stimuli‐responsive vehicles for targeted anticancer drug delivery.

show abstract

Complete pH-Dependent Shape Recovery in Cubical Hydrogel Capsules after Large Osmotic Deformations

Cited by 9 publications

References 67 publications

How Softness Matters in Soft Nanogels and Nanogel Assemblies

How Softness Matters in Soft Nanogels and Nanogel Assemblies

Two-Dimensional and Three-Dimensional Ultrathin Multilayer Hydrogels through Layer-by-Layer Assembly

Multilayer Hydrogel Microcubes: Effects of Templating Particle Morphology on Cubic Hydrogel Properties

Contact Info

Product

Resources

About