arXiv subjects

R. Angelini

Publications and source records attributed to R. Angelini.

12 recordsLinked to original sources

arXiv2023

Aging behavior of the localization length in a colloidal glass

The localization length r_{loc} associated with a fast secondary relaxation in glassy Laponite is determined by X-ray photon correlation spectroscopy (XPCS) through a Debye-Waller fit of the non-ergodicity parameter. Quantitative differences are observed between the time dependence (aging) of r_{loc} in spontaneously aged and rejuvenated samples. This behavior is also reflected in the calculated shear modulus which matches well with data obtained by rheological measurements.

cond-mat.soft↗

arXiv2023

Structural and Microscopic Relaxation Processes in Liquid Hydrogen Fluoride

The high frequency collective dynamics of liquid hydrogen fluoride is studied by inelastic x-ray scattering on the coexistence curve at T = 239 K. The comparison with existing molecular dynamics simulations shows the existence of two active relaxation processes with characteristic time scales in the subpicosecond range. The observed scenario is very similar to that found in liquid water. This suggests that hydrogen bonded liquids behave similarly to other very different systems as simple and glass forming liquids, thus indicating that these two relaxation processes are universal features of the liquid state.

cond-mat.soft↗

arXiv2022

Halting hyaluronidase activity with hyaluronan-based nanohydrogels: development of versatile injectable formulations

Hyaluronan (HA) is among the most used biopolymers for viscosupplementation and cosmetic applications. However, the current injectable HA-based formulations present relevant limitations: I) unmodified HA is quickly degraded by endogenous hyaluronidases (HAase), resulting in short lasting properties; II) cross-linked HA, although shows enhanced stability against HAase, often contains toxic chemical cross-linkers. As such, herein, we present biocompatible self-assembled hyaluronan-cholesterol nanohydrogels (HA-CH NHs) able to bind to HAase and inhibit the enzyme activity in vitro, more efficiently than currently marketed HA-based cross-linked formulations (e.g. JonexaTM). HA-CH NHs inhibit HAase through a mixed mechanism, by which NHs bind to HAase with an affinity constant 7-fold higher than that of HA. Similar NHs, based on gellan-cholesterol, evidenced no binding to HAase, neither inhibition of the enzyme activity, suggesting this effect might be due to the specific binding of HA-CH to the active site of the enzyme. Therefore, HA-CH NHs were engineered into injectable hybrid HA mixtures or physical hydrogels, able to halt the enzymatic degradation of HA.

cond-mat.soft↗

arXiv2022

The role of polymer structure on water confinement in poly(N-isopropylacrylamide) dispersions

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, in particular regarding crystallization and melting processes. In addition, we compare protiated and deuterated microgels, in both water and deuterated water. The DSC results are complemented by dynamic light scattering experiments, which confirm that the selective isotopic substitution differently affects the solution behaviour. Our findings highlight the important role played by the polymer architecture on the solution behaviour: indeed, microgels turn out to be more efficient confining agents, able to avoid water crystallization in a wider concentration range with respect to linear chains. Altogether, the present data will be valuable to interpret future low-temperature investigations of PNIPAM dispersions, particularly by neutron scattering experiments.

cond-mat.soft↗

arXiv2019

Gel and glass transition in fragile colloidal clays

Dynamic Light Scattering (DLS) measurements were performed on colloidal suspensions of Laponite\textsuperscript{\textregistered} at different concentrations in the range $C_\text{w}= (1.5{\div}3.0)$%. The slowing down of the dynamics induced by aging was monitored by following the temporal evolution of autocorrelation functions at different concentrations towards the gel and glass transition. Exploiting analogies with supercooled liquids approaching their glass transitions, an Angell plot for the structural relaxation times was drawn. Finally, the fragility of Laponite\textsuperscript{\textregistered} suspensions at different concentrations, in different solvents, at two salt concentrations and with the addition of a polymer was reported and discussed.

cond-mat.soft↗

arXiv2010

Competing interactions in arrested states of colloidal clays

Using experiments, theory and simulations, we show that the arrested state observed in a colloidal clay at intermediate concentrations is stabilized by the screened Coulomb repulsion (Wigner glass). Dilution experiments allow us to distinguish this high-concentration disconnected state, which melts upon addition of water, from a low-concentration gel state, which does not melt. Theoretical modelling and simulations reproduce the measured Small Angle X-Ray Scattering static structure factors and confirm the long-range electrostatic nature of the arrested structure. These findings are attributed to the different timescales controlling the competing attractive and repulsive interactions.

cond-mat.soft↗

arXiv2009

Shear thickening in molecular liquids characterized by inverse melting

We studied the rheological behavior of a molecular solution composed of $α$-cyclodextrin, water and 4-methylpyridine, a liquid known to undergo inverse melting, at different temperatures and concentrations. The system shows a marked non-Newtonian behavior, exhibiting the typical signature of shear thickening. Specifically, a transition is observed from a Newtonian to a shear thickening regime at a critical shear rate $\dotγ_c$. The value of this critical shear rate as a function of T follows an Arrhenius behavior $\dotγ_c(T)=$ B exp$(E_a/K_BT)$, with an activation energy $E_a$ close to the value of the hydrogen bond energy of the O-H group of the $α$-CD molecules. We argue that the increase of viscosity vs shear rate (shear thickening transition) is due to the formation of hydrogen bonded aggregates induced by the applied shear field. Finally, we speculate on the possible interplay between the non-Newtonian rheology and the inverse melting behavior, proposing a single mechanism to be at the origin of both phenomena.

cond-mat.soft↗

arXiv2008

Phase diagram of a solution undergoing inverse melting

The phase diagram of $α$-cyclodextrin/water/4-methylpyridine solutions, a system undergoing inverse melting, has been studied by differential scanning calorimetry, rheological methods, and X-rays diffraction. Two different fluid phases separated by a solid region have been observed in the high $α$-cyclodextrin concentration range ($c$$\geq$150 mg/ml). Decreasing $c$, the temperature interval where the solid phase exists decreases and eventually disappears, and a first order phase transition is observed between the two different fluid phases.

cond-mat.soft↗

arXiv2008

Arrested state of clay-water suspensions: gel or glass?

The aging of a charged colloidal system has been studied by Small Angle X-rays Scattering, in the exchanged momentum range Q=0.03 - 5 nm-1, and by Dynamic Light Scattering, at different clay concentrations (Cw =0.6 % - 2.8 %). The static structure factor, S(Q), has been determined as a function of both aging time and concentration. This is the first direct experimental evidence of the existence and evolution with aging time of two different arrested states in a single system simply obtained only by changing its volume fraction: an inhomogeneous state is reached at low concentrations, while a homogenous one is found at high concentrations.

cond-mat.soft↗

arXiv2006

High Frequency dynamics in metallic glasses

Using Inelastic X-ray Scattering we studied the collective dynamics of the glassy alloy Ni$_{33}$Zr$_{67}$ in the first pseudo Brillouin zone, an energy-momentum region still unexplored in metallic glasses. We determine key properties such as the momentum transfer dependence of the sound velocity and of the acoustic damping, discussing the results in the general context of recently proposed pictures for acoustic dynamics in glasses. Specifically, we demonstrate the existence in this strong glass of well defined (in the Ioffe Regel sense) acoustic-like excitations well above the Boson Peak energy.

cond-mat.dis-nn↗

arXiv2004

Microscopic dynamics and relaxation processes in liquid Hydrogen Fluoride

Inelastic x-ray scattering and Brillouin light scattering measurements of the dynamic structure factor of liquid hydrogen fluoride have been performed in the temperature range$ T=214\div 283 K$. The data, analysed using a viscoelastic model with a two timescale memory function, show a positive dispersion of the sound velocity $c(Q)$ between the low frequency value $c_0(Q)$ and the high frequency value $c_{\infty \alpha}(Q)$. This finding confirms the existence of a structural ($\alpha$) relaxation directly related to the dynamical organization of the hydrogen bonds network of the system. The activation energy $E_a$ of the process has been extracted by the analysis of the temperature behavior of the relaxation time $\tau_\alpha(T)$ that follows an Arrhenius law. The obtained value for $E_a$, when compared with that observed in another hydrogen bond liquid as water, suggests that the main parameter governing the $\alpha$-relaxation process is the number of the hydrogen bonds per molecule.

cond-mat.dis-nn↗

arXiv2003

Electron correlation effects on the dielectric function of liquid metals

The acoustic excitations of the expanded metal solutions Li-NH$_3$ have been measured by inelastic X-ray scattering as a function of the electron density by changing the Li concentration. The dielectric functions of these model metals with very low electron density have been derived from the high frequency sound velocity using the one component plasma approach corrected for screening. Their values, when combined with those from other metals, suggest that the electron correlation induced departure of the dielectric function from the random phase approximation follows a universal behavior whose main parameter is the electron density.

cond-mat↗