The phase behavior of poly (N-isopropylacrylamide) nanoparticles dispersed in aqueous medium is investigated as a function of temperature using static and dynamic light scattering techniques. The diameter, d of the particles, as determined by dynamic light scattering measurements on dilute dispersion showed a decrease in size from 273 nm at 25C to 114 nm at 40C as function of temperature with a sudden collapse of particle volume (volume phase transition) at 32.4C. Further this nanoparticle dispersion is found to turn turbid beyond volume phase transition. Static light scattering measurements on samples with intermediate concentration and high concentration showed liquid-like order and crystalline order respectively. The intensity of the Bragg peak of the crystallized sample when monitored as a function of temperature showed crystal to liquid transition at 26.2C and a fluid to fluid transition at 31C. The occurrence of melting at a volume fraction of 0.85 and the absence of change in number density across the fluid-to-fluid transition suggest that interparticle interaction is repulsive soft-sphere below the volume phase transition. The reported results on the phase behavior of poly(N-isopropylacrylamide) nanogel suspensions are discussed in the light of the present results.
Micro- and nanogels are widely used to stabilise emulsions and simultaneously implement their responsiveness to the external stimuli. One of the factors that improves the emulsion stability is the nanogel softness. Here, we study how the softest nanogels that can be synthesised with precipitation polymerisation of N-isopropylacrylamide (NIPAM), the ultra-low crosslinked (ULC) nanogels, stabilise oil-in-water emulsions. We show that ULC nanogels can efficiently stabilise emulsions already at low mass concentrations. These emulsions are resistant to droplet flocculation, stable against coalescen…
We study the effects of droplet finite size on the structure of nanogel particles synthesized by random crosslinking of molecular polymers diluted in nanoemulsions. For this, we use a bead-spring computer model of polymer-like structures that mimics the confined random crosslinking process corresponding to irradiation- or electrochemically-induced crosslinking methods. Our results indicate that random crosslinking under strong confinement can lead to unusual nanogel internal structures, with a central region less dense than the external one, whereas under moderate confinement the resulting str…
Using Langevin dynamics simulations, we investigate the self-assembly of magnetic nanogels in the presence of applied magneticfields of moderate strength. We find that even weak fields lead to drastic changes in the structure factors of both, the embeddedmagnetic nanoparticles and of whole nanogel particles. Nanogels assemble by uniting magnetic particle clusters forming inter-gelbridges. At zero field the average amount of such bridges for a pair of nanogels is close to one, whereas even for weak fields itfastly doubles. Rapid growth of cluster size at low values of the applied field is follo…
Collapse/expansion dynamics and actuation of pH-responsive nanogels
Research Center for Advanced Science and Technology, University of Tokyo（东京大学先进科学技术研究中心）；Department of Materials Science & Engineering, Johns Hopkins University（约翰斯·霍普金斯大学材料科学与工程系）
The encapsulation of fragile biomacromolecules is crucial for many biotechnological applications but remains challenging. Interfacial complexation (IC) in water-in-oil emulsions turned out to be an efficient process for the formation of protective polymer layers at the surface of capsule-precursor water droplets. We propose to further enhance this IC process by introducing thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) strands in the interfacial polymer layer. In this work, we implement surfactant-polymer IC in water-in-fluorocarbon oil emulsions between a water-soluble poly(L-lysine)-g…
Thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) particles of different sizes are synthesized by varying the concentration of sodium dodecyl sulphate (SDS) in a one-pot method. The sizes, size polydispersities and the thermoresponsivity of the PNIPAM particles are characterized by using dynamic light scattering and scanning electron microscopy. It is observed that the sizes of these particles decrease with increase in SDS concentration. Swelling ratios of PNIPAM particles measured from the thermoresponsive curves are observed to increase with decrease in particle size. This observation is…
Poly(N-isopropylacrylamide) (PNIPAM) is a synthetic polymer that is widely studied for its thermoresponsive character. However, recent works also reported evidence of a low temperature (protein-like) dynamical transition around 225 K in concentrated PNIPAM suspensions, independently of the polymer architecture, i.e., both for linear chains and for microgels. In this work, we investigate water-polymer interactions by extensive differential scanning calorimetry (DSC) measurements of both systems, in order to understand the effect of the different topological structures on the solution behaviour,…
Hypothesis: The peculiar swelling behaviour of poly(N-isopropylacrylamide) (PNIPAM)-based responsive microgels provides the possibility to tune both softness and volume fraction with temperature, making these systems of great interest for technological applications and theoretical implications. Their intriguing phase diagram can be even more complex if poly(acrylic acid) (PAAc) is interpenetrated within PNIPAM network to form Interpenetrating Polymer Network (IPN) microgels that exhibit an additional pH-sensitivity. The effect of the PAAc/PNIPAM polymeric ratio on both swelling capability and …
Poly(N-isopropylacrylamide), PNIPAM, is a widely studied polymer, which serves as a key constituent of nanostructured soft materials with responsive properties. Upon increasing temperature the PNIPAM polymer chain undergoes a reversible coil-to-globule transition at ~305K, which is reflected by a volume phase transition in cross-linked architectures, such as microgels, valuable for many practical applications. The addition of a cosolvent is a simple method to tune the transition temperature according to the specific purpose. In this study, we use atomistic molecular dynamics simulations to exp…
Poly-N-isopropylacrylamide (PNIPAM) is a thermoresponsive polymer, an essential building block of a large family of soft smart materials. In neat water it undergoes upon heating at $\approx$305K a phase transition from swollen to collapsed state. This interesting polymer behavior has been subject to a large number of computer modelling studies, mostly described with original OPLS force field suggested in the first works, where qualitatively correct behavior was observed. Nevertheless, employing converged replica exchange molecular dynamics simulations, we have shown on PNIPAM 30mer that this w…
Magnetic nanogels (MNG) -- soft colloids made of polymer matrix with embedded in it magnetic nanoparticles (MNPs) -- are promising magneto-controllable drug carriers. In order to develop this potential, one needs to clearly understand the relationship between nanogel magnetic properties and its behaviour in a hydrodynamic flow. Considering the size of the MNG and typical time and velocity scales involved in their nanofluidics, experimental characterisation of the system is challenging. In this work, we perform molecular dynamics (MD) simulations combined with the Lattice-Boltzmann (LB) scheme …
By means of atomistic molecular dynamics simulations we investigate the behaviour of poly(N-isopropylacrylamide), PNIPAM, in water at temperatures below and above the lower critical solution temperature (LCST), including the undercooled regime. The transition between water soluble and insoluble states at the LCST is described as a cooperative process involving an intramolecular coil-to-globule transition preceding the aggregation of chains and the polymer precipitation. In this work we investigate the molecular origin of such cooperativity and the evolution of the hydration pattern in the unde…
Poly(N-isopropylacrylamide)-based microgels are soft colloids undergoing a Volume Phase Transition (VPT) close to ambient temperature. Although widely employed for fundamental research and application purposes, the modifications of the microgel internal structure occurring at the VPT are not yet completely understood, especially concerning the role of electrostatics. Here we study in detail, both experimentally and numerically, the effect of the addition of acrylic acid (AAc) co-monomer on the microgel deswelling process. By combining viscosimetry, light scattering and electrophoresis, we show…
Hypotheses: Additives are commonly used to tune macromolecular conformational transitions. Among additives, trehalose is an excellent bioprotectant and among responsive polymers, PNIPAM is the most studied material. Nevertheless, their interaction mechanism so far has only been hinted without direct investigation, and, crucially, never elucidated in comparison to proteins. Detailed insights would help understand to what extent PNIPAM microgels can effectively be used as synthetic biomimetic materials, to reproduce and study, at the colloidal scale, isolated protein behavior and its sensitivity…
Temperature-sensitive hydrogels based on polymers such as poly(N-isopropylacrylamide) (PNIPAM) undergo a volume phase transition in response to changes in temperature. During this transition, distinct changes in both thermal and mechanical properties are observed. Here, we illustrate and exploit the inherent thermodynamic link between thermal and mechanical properties by showing that the compressive elastic modulus of PNIPAM hydrogels can be probed using differential scanning calorimetry. We validate our approach by using conventional osmotic compression tests. Our method could be particularly…
Combining elastic incoherent neutron scattering experiments at different resolutions with molecular dynamics simulations, we report the observation of a protein-like dynamical transition in linear chains of Poly(N-isopropylacrylamide). We identify the onset of the transition at a temperature $T_d$ of about 225~K. Thanks to a novel global fit procedure, we find quantitative agreement between measured and calculated polymer mean-squared displacements at all temperatures and time resolutions. Our results confirm the generality of the dynamical transition in macromolecular systems in aqueous envir…
Microgel particles composed of Interpenetrated Polymer Networks (IPN) of poly(N-isopropylacrylamide) (PNIPAM) and poly(acrylic acid) (PAAc) dispersed in water have been investigated through dynamic light scattering. The study of the temperature, concentration and pH dependence of the relaxation time has highlighted the existence of a thermoreversible transition corresponding to the swollen-shrunken volume phase transition. The presence of PAAc introduces an additional pH-sensitivity with respect to the temperature-sensitivity due to PNIPAM and leads to interesting differences in the transition…
We report temperature-responsive soft composites of semiflexible biopolymer networks (fibrin) containing dispersed microgel colloidal particles of poly(N-isopropylacrylamide) (pNIPAM) that undergo a thermodynamically driven de-swelling transition above a Lower Critical Solution Temperature (LCST). Unlike standard polymer-particle composites, decreasing the inclusion volume of the particles (by increasing temperature)is concomitant with a striking increase of the overall elastic stiffness of the composite. We observe such a behavior over a wide composition space. The composite elastic shear mod…
We construct colloidal ``sticky'' rods from the semi-flexible filamentous fd virus and temperature-sensitive polymers poly(N-isopropylacrylamide) (PNIPAM). The phase diagram of fd-PNIPAM system becomes independent of ionic strength at high salt concentration and low temperature, i.e. the rods are sterically stabilized by the polymer. However, the network of sticky rods undergoes a sol-gel transition as the temperature is raised. The viscoelastic moduli of fd and fd-PNIPAM suspensions are compared as a function of temperature, and the effect of ionic strength on the gelling behavior of fd-PNIPA…
We discuss the nonlinear rheology of dense colloidal dispersions at the glass transition. A first principles approach starting with interacting Brownian particles in given arbitrary homogeneous (incompressible) flow neglecting hydrodynamic interactions is sketched. It e.g. explains steady state flow curves for finite shear rates measured in dense suspensions of thermosensitive core-shell particles consisting of a polystyrene core and a crosslinked poly(N-isopropylacrylamide)(PNIPAM) shell. The exponents of simple and generalized Herschel Bulkley laws are computed for hard spheres.
Poly-N-isopropylacrylamide (PNIPAM) phase diagram is explored in a wide range of temperature and pressure using extensive all-atom molecular dynamics simulations. By exploiting a simple model of an atactic linear polymer chain, we provide novel insights into PNIPAM coil-to-globule transition addressing the roles played by both temperature and pressure. We find that a coil-to-globule transition exists up to large pressures, undergoing an intriguing reentrant behavior of the lower critical solution temperature with increasing pressure in agreement with experimental observations. Furthermore, we …
Responsive microgels based on poly(N-isopropylacrylamide) (PNIPAM) exhibit peculiar behaviours due to the competition between the hydrophilic and hydrophobic interactions of the constituent networks. The interpenetration of poly-acrilic acid (PAAc), a pH-sensitive polymer, within the PNIPAM network, to form Interpenetrated Polymer Network (IPN) microgels, affects this delicate balance and the typical Volume-Phase Transition (VPT) leading to complex behaviours whose molecular nature is still completely unexplored. Here we investigate the molecular mechanism driving the VPT and its influence on …
To explore dense packings of soft colloids, scattering experiments are ideal to access the structure factor. However, for soft microgels determination of the structure factor is difficult because of the low contrast of the polymer network and potential microgel interpenetration and deformation that change the form factor contribution. Here, we employ small-angle X-ray scattering (SAXS) to study soft, thermoresponsive microgels with poly-N-isopropylacrylamide (PNIPAM) shells and gold nanoparticle cores. The scattering of the gold cores dominates the scattering patterns and allows precise determ…
The volume phase transition of microgels is one of the most paradigmatic examples of stimuli-responsiveness, enabling a collapse from a highly swollen microgel state into a densely coiled state by an external stimulus. Although well characterized in bulk, it remains unclear how the phase transition is affected by the presence of a confining interface. Here, we demonstrate that the temperature-induced volume phase transition of poly(N-isopropylacrylamide) microgels, conventionally considered an intrinsic molecular property of the polymer, is in fact largely suppressed when the microgel is adsor…
We consider a model dense colloidal dispersion at the glass transition, and investigate the connection between equilibrium stress fluctuations, seen in linear shear moduli, and the shear stresses under strong flow conditions far from equilibrium, viz. flow curves for finite shear rates. To this purpose thermosensitive core-shell particles consisting of a polystyrene core and a crosslinked poly(N-isopropylacrylamide)(PNIPAM) shell were synthesized. Data over an extended range in shear rates and frequencies are compared to theoretical results from integrations through transients and mode couplin…
Interpenetrated polymer network microgels, composed of crosslinked networks of poly(N-isopropylacrylamide) and polyacrylic acid (PAAc), have been investigated through rheological measurements at four different amounts of polyacrylic acid. Both PAAc content and crosslinking degree modify particle dimensions, mass and softness, thereby strongly affecting the volume fraction and the system viscosity. Here the volume fraction is derived from the flow curves at low concentrations by fitting the zero-shear viscosity with the Einstein-Batchelor equation which provides a parameter k to shift weight co…
Thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) particles of a nearly constant swelling ratio and with polydispersity indices (PDIs) varying over a wide range (7.4% - 48.9%) are synthesized to study the effects of polydispersity on the dynamics of suspensions of soft PNIPAM colloidal particles. The PNIPAM particles are characterized using dynamic light scattering (DLS) and scanning electron microscopy (SEM). The zero shear viscosity ($η_{0}$) data of these colloidal suspensions, estimated from rheometric experiments as a function of the effective volume fraction $ϕ_{eff}$ of the suspensi…
Microcapsules allow for the controlled containment, transport, and release of cargoes ranging from pharmaceuticals to fragrances. Given the interest from a variety of industries in microcapsules and other core-shell structures, a multitude of fabrication strategies exist. Here, we report on a method relying on a mixture of temperature-responsive microgel particles, poly(N-isopropylacrylamide) (pNIPAM), and a polymer which undergo fluid-fluid phase separation. At room temperature this mixture separates into colloid-rich (liquid) and colloid-poor (gas) fluids. By heating the sample above a criti…
We investigate the conformation, position, and dynamics of core-shell nanoparticles (CSNPs) composed of a silica core encapsulated in a cross-linked poly-N-isopropylacrylamide shell at a water-oil interface for a systematic range of core sizes and shell thicknesses. We first present a free-energy model that we use to predict the CSNP wetting behavior at the interface as a function of its geometrical and compositional properties in the bulk phases, which gives good agreement with our experimental data. Remarkably, upon knowledge of the polymer shell deformability, the equilibrium particle posit…
A low-temperature dynamical transition has been reported in several proteins. We provide the first observation of a `protein-like' dynamical transition in nonbiological aqueous environments. To this aim we exploit the popular colloidal system of poly-N-isopropylacrylamide (PNIPAM) microgels, extending their investigation to unprecedentedly high concentrations. Owing to the heterogeneous architecture of the microgels, water crystallization is avoided in concentrated samples, allowing us to monitor atomic dynamics at low temperatures. By elastic incoherent neutron scattering and molecular dynami…
We combine small angle scattering experiments and simulations to investigate the internal structure and interactions of composite Poly(N-isopropylacrylamide)-Poly(ethylene glycol) (PNIPAM-PEG) microgels. At low temperatures the experimentally determined form factors and the simulated density profiles indicate a loose internal particle structure with an extended corona, that can be modeled as a star-like object. Increasing temperature across the volumetric phase transition, the form factor develops an inflection which, using simulations, is interpreted as arising from a configuration in which P…
The reconfiguration of soft, deformable particles upon adsorption at the interface between two fluids underpins many aspects of their dynamics and interactions, ultimately controlling the macroscopic properties of particle monolayers of relevance for materials, such as particle-stabilized emulsions and foams, and processes, e. g. particle-based lithography. In spite of its importance, experimentally determining the three-dimensional shape of soft particles at fluid interfaces with high resolution remains an elusive task. In this work, we take poly(N-isopropylacrylamide) (pNIPAM) microgels as m…
Responsive poly-N-isopropylacrylamide-based microgels are commonly used as model colloids with soft repulsive interactions. It has been shown that the microgel-microgel interaction in solution can be easily adjusted by varying the environmental parameters, e.g., temperature, pH, or salt concentration. Furthermore, microgels readily adsorb to liquid-gas and liquid-liquid interfaces forming responsive foams and emulsions that can be broken on-demand. In this work, we explore the interactions between microgel monolayers at the air-water interface and a hard colloid in the water. Force-distance cu…
Thermo-responsive microgel particles can exhibit a drastic volume shrinkage upon increasing the solvent temperature. Recently we found that the spreading of poly(N-isopropylacrylamide)(PNiPAm) microgels at a liquid interface under the influence of surface tension hinders the temperature-induced volume phase transition. In addition, we observed a hysteresis behavior upon temperature cycling, i.e. a different evolution in microgel size and shape depending on whether the microgel was initially adsorbed to the interface in expanded or collapsed state. Here, we model the volume phase transition of …
Soft particles such as microgels and core-shell particles can undergo significant and anisotropic deformations when adsorbed to a liquid interface. This, in turn, leads to a complex phase behavior upon compression. Here we develop a multiscale framework to rationally link the molecular particle architecture to the resulting interfacial morphology and, ultimately, to the collective interfacial phase behavior, enabling us to identify the key single-particle properties underlying two-dimensional continuous, heterostructural, and isostructural solid-solid transitions. Our approach resolves existin…
The key parameter controlling the glass transition of colloidal suspensions is $φ$, the fraction of the sample volume occupied by the particles. Unfortunately, changing $φ$ by varying an external parameter, \textit{e.g.} temperature $T$ as in molecular glass formers, is not possible, unless one uses thermosensitive colloidal particles, like the popular poly(N-isopropylacrylamide) (PNiPAM) microgels. These however have several drawbacks, including high deformability, osmotic deswelling and interpenetration, which complicate their use as a model system to study the colloidal glass transition. He…
