Glass and Jamming Rheology in Soft Particles Made of PNIPAM and Polyacrylic Acid.

The phase behaviour of soft colloids has attracted great attention due to the large variety of new phenomenologies emerging from their ability to pack at very high volume fractions. Here we report rheological measurements on interpenetrated polymer network microgels composed of poly(N-isopropylacrylamide) (PNIPAM) and polyacrylic acid (PAAc) at fixed PAAc content as a function of weight concentration. We found three different rheological regimes characteristic of three different states: a Newtonian shear-thinning fluid, an attractive glass characterized by a yield stress, and a jamming state. We discuss the possible molecular mechanisms driving the formation of these states.

Interpenetrating Polymer Network Microgels in Water: Effect of Composition on the Structural Properties and Electrosteric Interactions.

Microgels of cross-linked interpenetrating polymer networks (IPNs) are very versatile systems combining the properties of colloids and polymers. Herein we study IPN microgels composed of poly(N-isopropylacrylamide) and poly(acrylic acid) to understand how weight composition and reactant concentrations affect their structural, conformational and electrosteric properties in water. The results show that it is possible to drive the formation of microgels with the desired properties by adjusting IPN composition and preparation method during the synthesis. During synthesis, the polymerization of acrylic acid triggers the merging among IPNs via covalent linking, giving rise to microgels with larger mass and size, the effect being larger for higher concentration of the reactants. In addition, a close relation between the microgel internal conformation and the colloidal stability is observed, due to the presence of screened groups inside the microgel.

Keratin-PNIPAM Hybrid Microgels: Preparation, Morphology and Swelling Properties.

Combinations of synthetic polymers, such as poly(N-isopropylacrylamide) (PNIPAM), with natural biomolecules, such as keratin, show potential in the field of biomedicine, since these hybrids merge the thermoresponsive properties of PNIPAM with the bioactive characteristics of keratin. This synergy aims to produce hybrids that can respond to environmental stimuli while maintaining biocompatibility and functionality, making them suitable for various medical and biotechnological uses. In this study, we exploit keratin derived from wool waste in the textile industry, extracted via sulfitolysis, to synthesize hybrids with PNIPAM microgel. Utilizing two distinct methods-polymerization of NIPAM with keratin (HYB-P) and mixing preformed PNIPAM microgels with keratin (HYB-M)-resulted in hybrids with 20% and 25% keratin content, respectively. Dynamic light scattering (DLS) and transmission electron microscopic (TEM) analyses indicated the formation of colloidal systems with particle sizes of around 110 nm for HYB-P and 518 nm for HYB-M. The presence of keratin in both systems, 20% and 25%, respectively, was confirmed by spectroscopic (FTIR and NMR) and elemental analyses. Distinct structural differences were observed between HYB-P and HYB-M, suggesting a graft copolymer configuration for the former hybrid and a complexation for the latter one. Furthermore, these hybrids demonstrated temperature responsiveness akin to PNIPAM microgels and pH responsiveness, underscoring their potential for diverse biomedical applications.

Water slowing down drives the occurrence of the low temperature dynamical transition in microgels.

The protein dynamical transition marks an increase in atomic mobility and the onset of anharmonic motions at a critical temperature (T d), which is considered relevant for protein functionality. This phenomenon is ubiquitous, regardless of protein composition, structure and biological function and typically occurs at large protein content, to avoid water crystallization. Recently, a dynamical transition has also been reported in non-biological macromolecules, such as poly(N-isopropyl acrylamide) (PNIPAM) microgels, bearing many similarities to proteins. While the generality of this phenomenon is well-established, the role of water in the transition remains a subject of debate. In this study, we use atomistic molecular dynamics (MD) simulations and elastic incoherent neutron scattering (EINS) experiments with selective deuteration to investigate the microscopic origin of the dynamical transition and distinguish water and PNIPAM roles. While a standard analysis of EINS experiments would suggest that the dynamical transition occurs in PNIPAM and water at a similar temperature, simulations reveal a different perspective, also qualitatively supported by experiments. From room temperature down to about 180 K, PNIPAM exhibits only modest changes of dynamics, while water, being mainly hydration water under the probed extreme confinement, significantly slows down and undergoes a mode-coupling transition from diffusive to activated. Our findings therefore challenge the traditional view of the dynamical transition, demonstrating that it occurs in proximity of the water mode-coupling transition, shedding light on the intricate interplay between polymer and water dynamics.

Toward a Unified Description of the Electrostatic Assembly of Microgels and Nanoparticles.

The interplay of soft responsive particles, such as microgels, with nanoparticles (NPs) yields highly versatile complexes that show great potential for applications, ranging from plasmonic sensing to catalysis and drug delivery. However, the microgel-NP assembly process has not been investigated so far at the microscopic level, thus hindering the possibility of designing such hybrid systems a priori. In this work, we combine state-of-the-art numerical simulations with experiments to elucidate the fundamental mechanisms taking place when microgel-NP assembly is controlled by electrostatic interactions and the associated effects on the structure of the resulting complexes. We find a general behavior where, by increasing the number of interacting NPs, the microgel deswells up to a minimum size after which a plateau behavior occurs. This occurs either when NPs are mainly adsorbed to the microgel corona via the folding of the more external chains or when NPs penetrate inside the microgel, thereby inducing a collective reorganization of the polymer network. By varying microgel properties, such as fraction of cross-linkers or charge, as well as NP size and charge, we further show that the microgel deswelling curves can be rescaled onto a single master curve, for both experiments and simulations, demonstrating that the process is entirely controlled by the charge of the whole microgel-NP complex. Our results thus have a direct relevance in fundamental materials science and offer novel tools to tailor the nanofabrication of hybrid devices of technological interest.

Molecular origin of the two-step mechanism of gellan aggregation.

Among hydrocolloids, gellan is one of the most studied polysaccharides due to its ability to form mechanically stable gels. Despite its long-standing use, the gellan aggregation mechanism is still not understood because of the lack of atomistic information. Here, we fill this gap by developing a new gellan force field. Our simulations offer the first microscopic overview of gellan aggregation, detecting the coil to single-helix transition at dilute conditions and the formation of higher-order aggregates at high concentration through a two-step process: first, the formation of double helices and then their assembly into superstructures. For both steps, we also assess the role of monovalent and divalent cations, complementing simulations with rheology and atomic force microscopy experiments and highlighting the leading role of divalent cations. These results pave the way for future use of gellan-based systems in a variety of applications, from food science to art restoration.

Thermal Behaviour of Microgels Composed of Interpenetrating Polymer Networks of Poly(N-isopropylacrylamide) and Poly(acrylic acid): A Calorimetric Study.

Stimuli-responsive microgels have recently attracted great attention in fundamental research as their soft particles can be deformed and compressed at high packing fractions resulting in singular phase behaviours. Moreover, they are also well suited for a wide variety of applications such as drug delivery, tissue engineering, organ-on-chip devices, microlenses fabrication and cultural heritage. Here, thermoresponsive and pH-sensitive cross-linked microgels, composed of interpenetrating polymer networks of poly(N-isopropylacrylamide) (PNIPAM) and poly(acrylic acid) (PAAc), are synthesized by a precipitation polymerization method in water and investigated through differential scanning calorimetry in a temperature range across the volume phase transition temperature of PNIPAM microgels. The phase behaviour is studied as a function of heating/cooling rate, concentration, pH and PAAc content. At low concentrations and PAAc contents, the network interpenetration does not affect the transition temperature typical of PNIPAM microgel in agreement with previous studies; on the contrary, we show that it induces a marked decrease at higher concentrations. DSC analysis also reveals an increase of the overall calorimetric enthalpy with increasing concentration and a decrease with increasing PAAc content. These findings are discussed and explained as related to emerging aggregation processes that can be finely controlled by properly changing concentration, PAAc content an pH. A deep analysis of the thermodynamic parameters allows to draw a temperature-concentration state diagram in the investigated concentration range.

Chemical-Physical Behaviour of Microgels Made of Interpenetrating Polymer Networks of PNIPAM and Poly(acrylic Acid).

Microgels composed of stimuli responsive polymers have attracted worthwhile interest as model colloids for theorethical and experimental studies and for nanotechnological applications. A deep knowledge of their behaviour is fundamental for the design of new materials. Here we report the current understanding of a dual responsive microgel composed of poly(N-isopropylacrylamide) (PNIPAM), a temperature sensitive polymer, and poly(acrylic acid) (PAAc), a pH sensitive polymer, at different temperatures, PAAc contents, concentrations, solvents and pH. The combination of multiple techniques as Dynamic Light Scattering (DLS), Raman spectroscopy, Small Angle Neutron Scattering (SANS), rheology and electrophoretic measurements allow to investigate the hydrodynamic radius behaviour across the typical Volume Phase Transition (VPT), the involved molecular mechanism and the internal particle structure together with the viscoelastic properties and the role of ionic charge in the aggregation phenomena.

Thermoresponsivity of poly(N-isopropylacrylamide) microgels in water-trehalose solution and its relation to protein behavior.

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 to interactions with specific cosolvents or cosolutes. EXPERIMENTS: The effect of trehalose on the swelling behavior of PNIPAM microgels was monitored by dynamic light scattering; Raman spectroscopy and molecular dynamics simulations were used to explore changes of solvation and dynamics across the swelling-deswelling transition at the molecular scale. FINDINGS: Strongly hydrated trehalose molecules develop water-mediated interactions with PNIPAM microgels, thereby preserving polymer hydration below and above the transition while drastically inhibiting local motions of the polymer and of its hydration shell. Our study, for the first time, demonstrates that slowdown of dynamics and preferential exclusion are the principal mechanisms governing trehalose effect on PNIPAM microgels, at odds with preferential adsorption of alcohols, but in full analogy with the behavior observed in trehalose-protein systems.

Formation and Stability of Smooth Thin Films with Soft Microgels Made of Poly(N-Isopropylacrylamide) and Poly(Acrylic Acid).

In this work, soft microgels of Poly(N-Isopropylacrylamide) (PNIPAm) at two different sizes and of interpenetrated polymer network (IPN) composed of PNIPAm and Poly(Acrylic Acid) (PAAc) were synthesized. Then, solutions of these different types of microgels have been spin-coated on glass substrates with different degrees of hydrophobicity. PNIPAm particles with a larger diameter form either patches or a continuous layer, where individual particles are still distinct, depending on the dispersion concentration and spin speed. On the other, PNIPAm particles with a smaller diameter and IPN particles form a continuous and smooth film, with a thickness depending on the dispersion concentration and spin-speed. The difference in morphology observed can be explained if one considers that the microgels may behave as colloidal particles or macromolecules, depending on their size and composition. Additionally, the microgel size and composition can also affect the stability of the depositions when rinsed in water. In particular, we find that the smooth and continuous films show a stimuli-dependent stability on parameters such as temperature and pH, while large particle layers are stable under any condition except on hydrophilic glass by washing at 50 °C.

Poly(N-isopropylacrylamide) based thin microgel films for use in cell culture applications.

Poly(N-isopropylacrylamide) (PNIPAm) is widely used to fabricate cell sheet surfaces for cell culturing, however copolymer and interpenetrated polymer networks based on PNIPAm have been rarely explored in the context of tissue engineering. Many complex and expensive techniques have been employed to produce PNIPAm-based films for cell culturing. Among them, spin coating has demonstrated to be a rapid fabrication process of thin layers with high reproducibility and uniformity. In this study, we introduce an innovative approach to produce anchored smart thin films both thermo- and electro-responsive, with the aim to integrate them in electronic devices and better control or mimic different environments for cells in vitro. Thin films were obtained by spin coating of colloidal solutions made by PNIPAm and PAAc nanogels. Anchoring the films to the substrates was obtained through heat treatment in the presence of dithiol molecules. From analyses carried out with AFM and XPS, the final samples exhibited a flat morphology and high stability to water washing. Viability tests with cells were finally carried out to demonstrate that this approach may represent a promising route to integrate those hydrogels films in electronic platforms for cell culture applications.

Gellan Gum Microgels as Effective Agents for a Rapid Cleaning of Paper.

Microgel particles have emerged in the past few years as a favorite model system for fundamental science and for innovative applications ranging from the industrial to biomedical fields. Despite their potentialities, no works so far have focused on the application of microgels for cultural heritage preservation. Here we show their first use for this purpose, focusing on wet paper cleaning. Exploiting their retentive properties, microgels are able to clean paper, ensuring more controlled water release from the gel matrix, in analogy to their macroscopic counterpart, i.e., hydrogels. However, differently from these, the reduced size of microgels makes them suitable to efficiently penetrate in the porous structure of the paper and to easily adapt to the irregular surfaces of the artifacts. To test their cleaning abilities, we prepare microgels made of Gellan gum, a natural and widespread material already used as a hydrogel for paper cleaning, and apply them to modern and ancient paper samples. Combining several diagnostic methods, we show that microgels performances in the removal of cellulose degradation byproducts for ancient samples are superior to commonly employed hydrogels and water bath treatments. This is due to the composition and morphology of ancient paper, which facilitates microgels penetration. For modern paper cleaning, performances are at least comparable to the other methods. In all cases, the application of microgels takes place on a time scale of a few minutes, opening the way for widespread use as a rapid and efficient cleaning protocol.

Study of network composition in interpenetrating polymer networks of poly(N isopropylacrylamide) microgels: The role of poly(acrylic acid).

HYPOTHESIS: The peculiar swelling behaviour of poly(N-isopropylacrylamide) (PNIPAM)4-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)5 is interpenetrated within PNIPAM network to form Interpenetrating Polymer Network (IPN)6 microgels that exhibit an additional pH-sensitivity. The effect of the PAAc/PNIPAM polymeric ratio on both swelling capability and dynamics is still matter of investigation. EXPERIMENTS: Here we investigate the role of PAAc in the behaviour of IPN microgels across the volume phase transition through dynamic light scattering (DLS),7 transmission electron microscopy (TEM)8 and electrophoretic measurements as a function of microgel concentration and pH. FINDINGS: Our results highlight that aggregation is favored at increasing weight concentration, PAAc content and pH and that a crossover PAAc content CPAAc∗9 exists above which the ionic charges on the microgel become relevant. Moreover we show that the softness of IPN microgels can be tuned ad hoc by changing the PAAc/PNIPAM ratio. These findings provide new insights into the possibility to control experimentally aggregation properties, charge and softness of IPN microgels by varying PAAc content.

Evidence of a low-temperature dynamical transition in concentrated microgels.

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 dynamics simulations, we find that a dynamical transition occurs at a temperature T d ~ 250 K, independently from PNIPAM mass fraction. However, the transition is smeared out on approaching dry conditions. The quantitative agreement between experiments and simulations provides evidence that the transition occurs simultaneously for PNIPAM and water dynamics. The similarity of these results with hydrated protein powders suggests that the dynamical transition is a generic feature in complex macromolecular systems, independently from their biological function.