The unique pH and temperature responsiveness of PNIPAM-based microgels make them a promising target for novel biomedical applications such as cellular drug delivery systems. However, we lack a ...comprehensive understanding of how the physicochemical properties of microgels relate to their interaction with cells. Here, we show that HEK293T cells take up PNIPAM-based microgels on a second-to-minute time scale. Uptake rates are determined by microgel size and cross-linker content. Using fluorescence confocal live-cell microscopy, we observe microgel uptake in real time and describe cellular uptake kinetics. Experiments reveal that small and less cross-linked microgels show faster uptake kinetics than microgels of larger size or higher cross-linker content. Only microgels that are larger than 800 nm in diameter and have cross-linking contents of 10–15 mol % do not show translocation into cells. Together, these results provide insight into microgel–cell interactions and generate quantitative information on the deterministic role of microgel architecturei.e., size and rigidityfor uptake by a prototypical human cell line.
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Soft particles such as polymeric microgels can form ultra-dense phases, where the average center-to-center distance a
can be smaller than the initial unperturbed particle diameter σ
, due to their ...ability to interpenetrate and compress. However, despite of the effort devoted to microgels at ultrahigh densities, we know surprisingly little about their response to their environment at effective volume fractions ϕ
above close packing (ϕ
), and the existing information is often contradictory. Here we report direct measurements of the size and shape of poly(N-isopropylacrylamide) microgels at concentrations below and above ϕ
using the zero average contrast method in small-angle neutron scattering. We complement these experiments with measurements of the average interparticle distances using small-angle x-ray scattering, and a determination of the glass transition using dynamic light scattering. This allows us to unambiguously decouple interaction effects from density-dependent variations of the particle size and shape at all values of ϕ
. We demonstrate that the microgels used in this study significantly interpenetrate and thus change their size and shape only marginally even for ϕ
≫ ϕ
, a finding that may require changes in the interpretation of a number of previously published studies on the structural and dynamic properties of dense soft particle systems.
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We investigate the collective behavior of suspended thermoresponsive microgels that expel solvent and subsequently decrease in size upon heating. Using a binary mixture of differently ...thermoresponsive microgels, we demonstrate how distinctly different gel structures form, depending on the heating profile used. Confocal laser scanning microscopy (CLSM) imaging shows that slow heating ramps yield a core–shell network through sequential gelation, while fast heating ramps yield a random binary network through homogelation. Here, secondary particles are shown to aggregate in a monolayer fashion upon the first gel, which can be qualitatively reproduced through Brownian dynamics simulations using a model based on a temperature-dependent interaction potential incorporating steric repulsion and van der Waals attraction. Through oscillatory rheology it is shown that secondary microgel deposition enhances the structural integrity of the previously formed single species gel, and the final structure exhibits higher elastic and loss moduli than its compositionally identical homogelled counterpart. Furthermore, we demonstrate that aging processes in the scaffold before secondary microgel deposition govern the final structural properties of the bigel, which allows a detailed control over these properties. Our results thus demonstrate how the temperature profile can be used to finely control the structural and mechanical properties of these highly tunable materials.
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The interfacial structure of natural rubber (NR) colloids is investigated by means of cryogenic transmission electron microscopy (cryo-TEM) and electrokinetics over a broad range of KNO3 electrolyte ...concentrations (4–300 mM) and pH values (1–8). The asymptotic plateau value reached by NR electrophoretic mobility (μ) in the thin double layer limit supports the presence of a soft (ion- and water-permeable) polyelectrolytic type of layer located at the periphery of the NR particles. This property is confirmed by the analysis of the electron density profile obtained from cryo-TEM that evidences a ∼2–4 nm thick corona surrounding the NR polyisoprene core. The dependence of μ on pH and salt concentration is further marked by a dramatic decrease of the point of zero electrophoretic mobility (PZM) from 3.6 to 0.8 with increasing electrolyte concentration in the range 4–300 mM. Using a recent theory for electrohydrodynamics of soft multilayered particles, this “anomalous” dependence of the PZM on electrolyte concentration is shown to be consistent with a radial organization of anionic and cationic groups across the peripheral NR structure. The NR electrokinetic response in the pH range 1–8 is indeed found to be equivalent to that of particles surrounded by a positively charged ∼3.5 nm thick layer (mean dissociation pK ∼ 4.2) supporting a thin and negatively charged outermost layer (0.6 nm in thickness, pK ∼ 0.7). Altogether, the strong dependence of the PZM on electrolyte concentration suggests that the electrostatic properties of the outer peripheral region of the NR shell are mediated by lipidic residues protruding from a shell containing a significant amount of protein-like charges. This proposed NR shell interfacial structure questions previously reported NR representations according to which the shell consists of either a fully mixed lipid–protein layer, or a layer of phospholipids residing exclusively beneath an outer proteic film.
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A simple procedure is developed to probe in situ the association between lipid bilayers and colloidal particles. Here, a one-step method is applied to generate giant unilamellar ...1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) vesicles (GUVs) by application of an alternating electric field directly in the presence of thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) microgels. We demonstrate that the soft PNIPAM microgel particles act as switchable stabilizers for lipid membranes. The change of the particle conformation from the swollen to the collapsed state enables the reversible control of the microgel adsorption as a function of temperature. At 20 °C, the swollen and hydrophilic soft microgel particles adsorb evenly and densely pack in 2D hexagonal arrays at the DOPC GUV surfaces. In contrast, at 40 °C, that is, above the volume phase transition temperature (T VPT = 32 °C) of the PNIPAM microgels, the collapsed and more hydrophobic particles partially desorb and self-organize into domains at the GUV/GUV interfaces. This study shows that thermoresponsive PNIPAM microgels can be used to increase and control the stability of lipid vesicles where the softness and deformability of these types of particles play a major role. The observed self-assembly, where the organization and position of the particles on the GUV surface can be controlled “on demand”, opens new routes for the design of nanostructured materials.
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Thermoresponsive microgels are soft colloids that find widespread use as model systems for soft matter physics. Their complex internal architecture, made of a disordered and heterogeneous polymer ...network, has been so far a major challenge for computer simulations. In this work, we put forward a coarse-grained model of microgels whose structural properties are in quantitative agreement with results obtained with small-angle X-ray scattering experiments across a wide range of temperatures, encompassing the volume phase transition. These results bridge the gap between experiments and simulations of individual microgel particles, paving the way to theoretically address open questions about their bulk properties with unprecedented nano- and microscale resolution.
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Nature suggests that complex materials result from a hierarchical organization of matter at different length scales. At the nano- and micrometer scale, macromolecules and supramolecular aggregates ...spontaneously assemble into supracolloidal structures whose complexity is given by the coexistence of various colloidal entities and the specific interactions between them. Here, we demonstrate how such control can be implemented by engineering specially customized bile salt derivative-based supramolecular tubules that exhibit a highly specific interaction with polymeric microgel spheres at their extremities thanks to their scroll-like structure. This design allows for hierarchical supracolloidal self-assembly of microgels and supramolecular scrolls into a regular framework of “nodes” and “linkers”. The supramolecular assembly into scrolls can be triggered by pH and temperature, thereby providing the whole supracolloidal system with interesting stimuli-responsive properties. A colloidal smart assembly is embodied with features of center-linker frameworks as those found in molecular metal–organic frameworks and in structures engineered at human scale, masterfully represented by the Atomium in Bruxelles.
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Small clusters of spherical colloids that mimic real molecules, so-called colloidal molecules, hold great promise as building blocks in bottom-up routes to new materials. However, their typical hard ...sphere nature has hampered their assembly into ordered structures, largely due to a lack of control in the interparticle interactions. To provide easy external control of the interactions, the present work focuses on the preparation of colloidal molecules from temperature-responsive microgel particles that undergo a transition from a soft repulsive to a short-range attractive state as their characteristic volume phase transition temperature (VPTT) is crossed. Preparation of the colloidal molecules starts with the use of a droplet-based microfluidics device to form highly uniform water-in-oil (W/O) emulsion droplets containing, on average and with a narrow distribution, four microgels per droplet. Evaporation of the water then leads to the formation of colloidal molecule-like clusters, which can be harvested following cross-linking and phase transfer. We use a mixture of two types of microgels, one based on poly(N-isopropylacrylamide) (PNIPAM) and the other on poly(N-isopropylmethacrylamide) (PNIPMAM), to prepare bicomponent colloidal molecules, and show that the difference in VPTT between the two allows for induction of attractive interparticle interactions between the PNIPAM interaction sites at temperatures in between the two VPTTs, analogous to the interactions among patchy biomacromolecules such as many proteins.
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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.
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Microgels, cross-linked polymers with submicrometer size, are ideal soft model systems. While spherical microgels have been studied extensively, anisotropic microgels have hardly been investigated. ...In this study, we compare the interfacial deformation and assembly of anisotropic core–shell and hollow microgels. The core–shell microgel consists of an elliptical core of hematite covered with a thin silica layer and a thin shell made of poly(N-isopropylacrylamide). The hollow microgels were obtained after a two-step etching procedure of the inorganic core. The behavior of these microgels at the oil–water interface was investigated in a Langmuir–Blodgett trough combined with ex situ atomic force microscopy. First, the influence of the architecture of anisotropic microgels on their spreading at the interface was investigated experimentally and by dissipative particle dynamic simulations. Hereby, the importance of the local shell thickness on the lateral and longitudinal interfacial deformation was highlighted as well as the differences between the core–shell and hollow architectures. The shape of the compression isotherms as well as the dimensions, ordering, and orientation of the microgels at the different compressions were analyzed. Due to their anisotropic shape and stiffness, both anisotropic microgels were found to exhibit significant capillary interactions with a preferential side-to-side assembly leading to stable microgel clusters at low interfacial coverage. Such capillary interactions were found to decrease in the case of the more deformable hollow anisotropic microgels. Consequently, anisotropic hollow microgels were found to distribute more evenly at high surface pressure compared to stiffer core–shell microgels. Our findings emphasize the complex interplay between the colloid design, anisotropy, and softness on the interfacial assembly and the opportunities it therefore offers to create more complex ordered interfaces.
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