arXiv subjects

Elena Buratti

Publications and source records attributed to Elena Buratti.

13 recordsLinked to original sources

arXiv2026

Heterogeneous collapse in thermoresponsive copolymer microgels varying molar composition

Understanding the internal architecture of copolymer microgels is crucial for establishing how nanoscale polymer organization controls their stimuli-responsive behavior. Here we focus on thermoresponsive P(N-isopropylacrylamide-co-N-isopropyl-methacrylamide), P(NIPAM-co-NIPMAM), microgels with varying mole fraction of the components, synthesized via radical precipitation polymerization, and we demonstrate that changes in their volume phase transition and equilibrium swelling are governed by composition-dependent internal heterogeneity. Comparison between small-angle neutron scattering (SANS) with isotopic labeling and monomer-resolved simulations show a block-like monomer distribution of the two components. SANS analysis reveals a universal maximum in the polymer mesh correlation length near the transition, evidencing coexistence of collapsed NIPAM-rich and swollen domains. The correlation length increases with increasing NIPMAM content, with a maximum for 75 mol \% NIPMAM, implying sparse collapsed regions within the network and thus a large degree of heterogeneity induced by the presence of an increasingly large fraction of intercalated, non-collapsing PNIPMAM. The maximum heterogeneity correlates with the equilibrium swelling ratio, indicating that collapsed microgels retain a structural memory of the transition and present a less-compliant structure in response to temperature variations. Overall, these insights highlight a complex effect of the block-like monomer distribution on the responsive properties of copolymer microgels with different compositions, thus providing a design rule for tailoring responsive colloids for functional soft materials.

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arXiv2025

Thermoresponsive copolymer microgels synthesized via single-step precipitation polymerization: random or block structure?

The inner structure of polymeric particles critically influences their phase behavior and functionality, governing their mechanical properties and their physical and chemical interactions. For thermoresponsive microgels, i.e. colloidal particles comprising a crosslinked polymer network that undergo a volume transition upon temperature changes, structural control is key to tailor the material responsivity and broaden the range of applications. In this work, we present a comprehensive investigation of the internal structure of poly(N-isopropylacrylamide-co-N-isopropylmethacrylamide), P(NIPAM-co-NIPMAM), copolymer microgels, combining small-angle neutron scattering (SANS), dynamic light scattering (DLS), and nuclear magnetic resonance (NMR) measurements with multi-scale simulations. By synthesizing different samples, we probe the microgels swelling behavior, revealing distinct signatures of the individual polymers. To elucidate their internal distribution, we perform monomer-resolved microgel simulations across different copolymer models. A direct comparison between experimental and numerical form factors under different, neutron-selective conditions provides evidence of a preferential organization into block structures rather than a random arrangement. These results are confirmed by 13C-NMR which reveals the clear presence of NIPAM blocks within a more random arrangement of the remaining monomers and by atomistic molecular dynamics simulations on copolymer chains, which also shed light on a possible origin in the dependence of the hydrogen bonding capability on the local environment. These findings provide a detailed microscopic picture of the inner architecture of P(NIPAM-co-NIPMAM) microgels, revealing an unexpected structural organization that may be generalized to other copolymer systems and could be promising to tailor microgel design and enhance control of material responsivity.

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arXiv2024

Gellan-Based Hydrogels and Microgels for culturage heritage: a rheological perspective

Gellan gum has gained significant attention due to its versatility in multiple applications in the form of hydrogels and microgels. A thorough understanding of the rheological behaviour of these systems is crucial both for fundamental research and to optimize the manufacturing needs. To this aim, here we extensively characterize the rheological behaviour of gellan based hydrogels and microgels recently used for efficient paper cleaning for restoration interventions. In particular, we study their viscoelastic properties, also during hydrogel and microgel formation, assessing the role of temperature, gellan concentration, and, importantly, the presence of different cations, which plays a crucial role in the gelation process. We find the interesting result that, in the conditions where they are efficient for cleaning, gellan hydrogels exhibit a double yielding behavior. In addition, we provide a detailed description of gellan microgels preparation, ensuring high control and reproducibility of the samples. Altogether our study sheds light on the mechanical stability, network structure, and overall functionality of the gellan-based gels, providing valuable insights into optimizing conditions for desired applications in paper cleaning.

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arXiv2023

Apparatus for simultaneous DLS-SANS investigations of dynamics and structure in soft matter

Dynamic Light Scattering (DLS) and Small-Angle Neutron Scattering (SANS) are two key tools with which to probe the dynamic and static structure factor, respectively, in soft matter. Usually DLS and SANS measurements are performed separately, in different laboratories, on different samples and at different times. However, this methodology has particular disadvantages for a large variety of soft materials which exhibit high sensitivity to small changes in fundamental parameters such as waiting times, concentration, pH, ionic strength, etc. Here we report on a new portable DLS-SANS apparatus that allows one to simultaneously measure both the microscopic dynamics (through DLS) and the static structure (through SANS) on the same sample. The apparatus has been constructed as a collaboration between two laboratories, each an expert in one of the scattering methods, and was commissioned on the \textit{LOQ} and \textit{ZOOM} SANS instruments at the ISIS Pulsed Neutron \& Muon Source, U.K.

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arXiv2023

Toward a unified description of the electrostatic assembly of microgels and nanoparticles

The combination of soft responsive particles, such as microgels, with nanoparticles (NPs) yields highly versatile complexes of great potential for applications, from ad-hoc plasmonic sensors to controlled protocols for loading and release. However, the assembly process between these microscale networks and the co-dispersed nano-objects has not been investigated so far at the microscopic level, preempting the possibility of designing such hybrid complexes a priori. In this work, we combine state-of-the-art numerical simulations with experiments, to elucidate the fundamental mechanisms taking place when microgels-NPs assembly is controlled by electrostatic interactions. 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 crosslinkers or charge, as well as NPs 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-NPs 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.

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arXiv2023

Relaxation dynamics, Softness and Fragility of Microgels with Interpenetrated Polymer Networks

Microgels are elastic and deformable particles with a hybrid nature between that of polymers and colloids and unconventional behaviours with respect to hard colloids. We investigated the dynamics of a soft microgel made of interpenetrated polymer networks of PNIPAM and PAAc by means of coherent X-ray and light scattering techniques. By varying the particle softness through PAAc content we can tune at wish the fragility of IPN microgels. Interestingly we find the occurrence of a dynamical crossover at a critical weight concentration which leads to an evolution of the structural relaxation time from a super-Arrhenius to a slower than Arrhenius behaviour, a minimum for the shape parameter of intensity autocorrelation function and the emerging of distinct anomalous mechanisms for particle motion. This complex phenomenology can be described by a Fickian diffusion at very low concentrations, an effective non Fickian anomalous diffusion at intermediate values and a ballistic motion well described within the Mode Coupling Theory.

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arXiv2022

Molecular origin of the two-step mechanism of gellan aggregation

Among hydrocolloids, gellan is one of the most used anionic polysaccharides, because of its capability of forming mechanically stable gels at relatively low concentrations. Despite its long-standing use and importance, the gellan aggregation mechanism is still not presently understood at the microscopic level due to the lack of atomistic information. Here we will fill this gap by reporting molecular dynamics simulations of gellan chains at different polymer and salt contents, being able to unveil the occurrence of the two steps in the process, in agreement with existing hypotheses. At first, the formation of double helices takes place, followed by the aggregation into super-structures. For both steps, the role of bivalent cations appears to be crucial, as also shown by rheology and atomic force microscopy measurements: they not only facilitate the junction of the chains into double helices, but also promote through bridging their arrangement into larger aggregates. On the other hand, monovalent cations have a much more reduced role, making it possible to form double helices only at very high salt content and not actively participating in the formation of gels. Our simulations thus offer the first complete microscopic overview of gellan aggregation and will be important for future use of gellan-based systems for a wide variety of applications, ranging from food science to art restoration.

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arXiv2022

Volume fraction determination of microgel composed of interpenetrating polymer networks of PNIPAM and polyacrylic acid

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 concentration to volume fraction. We find that particles with higher PAAc content and crosslinker are characterized by a greater value of k and therefore by larger volume fractions when compared to softer particles. The packing fractions obtained from rheological measurements are compared with those from static light scattering for two PAAc contents revealing a good agreement. Moreover, the behaviour of the viscosity as a function of packing fraction, at room temperature, has highlighted an Arrhenius dependence for microgels synthesized with low PAAc content and a Vogel-Fulcher-Tammann dependence for the highest investigated PAAc concentration. A comparison with the hard spheres behaviour indicates a steepest increase of the viscosity with decreasing particles softness. Finally, the volume fraction dependence of the viscosity at a fixed PAAc and at two different temperatures, below and above the volume phase transition, shows a quantitative agreement with the structural relaxation time measured through dynamic light scattering indicating that IPN microgels softness can be tuned with PAAc and temperature and that, depending on particle softness, two different routes are followed.

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arXiv2022

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(Nisopropylacrylamide) (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.

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arXiv2022

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.

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arXiv2019

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)-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 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), transmission electron microscopy (TEM) 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 C*_{PAAc} 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.

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arXiv2019

Molecular mechanisms driving the microgels behaviour: a Raman spectroscopy and Dynamic Light Scattering study

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 particle aggregation for PNIPAM/PAAc IPN microgels by the joint use of Dynamic Light Scattering and Raman Spectroscopy. Our results highlight that PNIPAM hydrophobicity is enhanced by the interpenetration of PAAc promoting interparticle interactions, a crossover concentration is found above which aggregation phenomena become relevant. Moreover we find that, at variance with PNIPAM, for IPN microgels a double-step molecular mechanisms occurs upon crossing the VPT, the first involving the coil-to-globule transition typical of PNIPAM and the latter associated to PAAc steric hindrance.

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arXiv2019

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 $T_d\sim250$~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.

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