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.

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.

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.

Understanding the metal free alginate gelation process.

Alginate is a natural polysaccharide that has been recently gaining increasing attention as a biomaterial in the field of tissue engineering due to its favourable biocompatibility and gelation properties. Alginate hydrogels are commonly made by ionic crosslinking in the presence of divalent cations. Only a few studies have attempted to prepare alginate hydrogels without the presence of metal cations. Here the formation of metal free alginate hydrogels in the presence of the amino-acid glutamine is investigated. The transition from sol to gel is monitored by rheological measurements in the viscoelastic regime that reveal how the charged or neutral form of glutamine induces deep differences in the gelling ability. In particular, we show that the storage, G', and loss, G'', moduli differ significantly by shifting the glutamine zwitterionic equilibrium. Protonated amino acid could induce a shielding effect of the electrostatic repulsion of the alginate chains. Stable gels are obtained in the presence of a larger amount of free organic acid that gives rise to chain crosslink junctions and chain-chain stabilization. This opens up the possibility of preparing metal-free alginate hydrogels based on amino acid equilibria being pH sensitive.

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.

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.

C-12 vs C-3 substituted bile salts: An example of the effects of substituent position and orientation on the self-assembly of steroid surfactant isomers.

Biomolecule derivatives are transversally used in nanotechnology. Deciphering their aggregation behavior is a crucial issue for the rational design of functional materials. To this end, it is necessary to build libraries of selectively functionalized analogues and infer general rules. In this work we enrich the highly applicative oriented collection of steroid derivatives, by reporting a rare example of C-12 selectively modified bile salt. While nature often exploits such position to encode functions, it is unusual and not trivial to prepare similar analogues in the laboratory. The introduction of a tert-butyl phenyl residue at C-12 provided a molecule with a self-assembly that remarkably switched from rigid pole-like structures to twisted ribbons at a biologically relevant critical temperature (∼25 °C). The system was characterized by microscopy and spectroscopy techniques and compared with the C-3 functionalized analogue. The twisted ribbons generate samples with a gel texture and a viscoelastic response. The parallel analysis of the two systems suggested that the observed thermoresponsive self-assemblies occur at similar critical temperatures and are probably dictated by the nature of the substituent, but involve aggregates with different structures depending on position and orientation of the substituent. This study highlights the self-assembly properties of two appealing thermoresponsive systems. Moreover, it adds fundamental insights hereto missing in the investigations of the relation between self-assembly and structure of synthetic steroids, which are valuable for the rational design of steroidal amphiphiles.

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.

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.

Dynamical behavior of microgels of interpenetrated polymer networks.

Microgel suspensions of an interpenetrated Polymer Network (IPN) of PNIPAM and PAAc in D2O have been investigated through dynamic light scattering as a function of temperature, pH and concentration across the Volume Phase Transition (VPT). The dynamics of the system is slowed down under H/D isotopic substitution due to different balance states between polymer/polymer and polymer/solvent interactions suggesting the crucial role played by H-bonding. The swelling behavior, reduced with respect to PNIPAM and water, has been described by the Flory-Rehner theory, tested for PNIPAM microgel and successfully expanded to higher order for IPN microgels. Moreover the concentration dependence of the relaxation time at neutral pH has highlighted two different routes to approach the glass transition: Arrhenius and super-Arrhenius (Vogel Fulcher Tammann) respectively below and above the VPT and a fragility plot has been derived. Fragility can be tuned by changing temperature: across the VPT particles undergo a transition from soft-strong to stiff-fragile.

Isotopic Effect on the Gel and Glass Formation of a Charged Colloidal Clay: Laponite.

The time evolution of both dynamic and static structure factors of a charged colloidal clay, Laponite, dispersed in both H2O and D2O solvents has been investigated through multiangle dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS) as a function of weight concentration. The aging phenomenology and the formation of arrested states, both gel and glass, are preserved in D2O, while the dynamics is slowed down with respect to water. These findings are important to understand the role played by the solvent in the interparticle interactions and for techniques such as neutron scattering and nuclear magnetic resonance that allow for the extension of the accessible scattering vectors and time scales.

Local structure of temperature and pH-sensitive colloidal microgels.

The temperature dependence of the local intra-particle structure of colloidal microgel particles, composed of interpenetrated polymer networks, has been investigated by small-angle neutron scattering at different pH and concentrations, in the range (299÷315) K, where a volume phase transition from a swollen to a shrunken state takes place. Data are well described by a theoretical model that takes into account the presence of both interpenetrated polymer networks and cross-linkers. Two different behaviors are found across the volume phase transition. At neutral pH and T ≈ 307 K, a sharp change of the local structure from a water rich open inhomogeneous interpenetrated polymer network to a homogeneous porous solid-like structure after expelling water is observed. Differently, at acidic pH, the local structure changes almost continuously. These findings demonstrate that a fine control of the pH of the system allows to tune the sharpness of the volume-phase transition.

Structural and microscopic relaxations in a colloidal glass.

The aging dynamics of a colloidal glass has been studied by multiangle dynamic light scattering, neutron spin echo, X-ray photon correlation spectroscopy and molecular dynamics simulations. The two relaxation processes, microscopic (fast) and structural (slow), have been investigated in an unprecedentedly wide range of time and length scales covering both ergodic and nonergodic regimes. The microscopic relaxation time remains diffusive at all length scales across the glass transition scaling with wavevector Q as Q(-2). The length-scale dependence of structural relaxation time changes from diffusive, characterized by a Q(-2)-dependence in the early stages of aging, to a Q(-1)-dependence in the full aging regime which marks a discontinuous hopping dynamics. Both regimes are associated with a stretched behaviour of the correlation functions. We expect these findings to provide a general description of both relaxations across the glass transition.

Glass-glass transition during aging of a colloidal clay.

Colloidal suspensions are characterized by a variety of microscopic interactions, which generate unconventional phase diagrams encompassing fluid, gel and glassy states and offer the possibility to study new phase and/or state transitions. Among these, glass-glass transitions are rare to be found, especially at ambient conditions. Here, through a combination of dilution experiments, X-ray photon correlation spectroscopy, small angle X-ray scattering, rheological measurements and Monte Carlo simulations, we provide evidence of a spontaneous glass-glass transition in a colloidal clay. Two different glassy states are distinguished with evolving waiting time: a first one, dominated by long-range screened Coulombic repulsion (Wigner glass) and a second one, stabilized by orientational attractions (Disconnected House of Cards glass), occurring after a much longer time. These findings may have implications for heterogeneously charged systems out-of-equilibrium and for applications where a fine control of the local order and/or long term stability of the amorphous materials are required.

Observation of empty liquids and equilibrium gels in a colloidal clay.

The relevance of anisotropic interactions in colloidal systems has recently emerged in the context of the rational design of new soft materials. Patchy colloids of different shapes, patterns and functionalities are considered the new building blocks of a bottom-up approach toward the realization of self-assembled bulk materials with predefined properties. The ability to tune the interaction anisotropy will make it possible to recreate molecular structures at the nano- and micro-scales (a case with tremendous technological applications), as well as to generate new unconventional phases, both ordered and disordered. Recent theoretical studies suggest that the phase diagram of patchy colloids can be significantly altered by limiting the particle coordination number (that is, valence). New concepts such as empty liquids­liquid states with vanishing density­and equilibrium gels­arrested networks of bonded particles, which do not require an underlying phase separation to form­have been formulated. Yet no experimental evidence of these predictions has been provided. Here we report the first observation of empty liquids and equilibrium gels in a complex colloidal clay, and support the experimental findings with numerical simulations.

Effects of two offshore gas platforms on soft-bottom benthic communities (northwestern Adriatic Sea, Italy).

The macrozoobenthos living around two offshore gas platforms, Barbara NW (pB) and Calipso (pC) located in the northwestern Adriatic Sea were investigated for three years after their construction to detect eventual effects due to the platforms. The sampling stations were spaced at increasing distance from the platforms up to 1000 m. Both multivariate and univariate analysis showed an initial defaunation (short-term effect) at pB and within a 120 m radius at pC. A general recovery in terms of abundance, species richness and diversity was observed for the benthic communities after one year. During the third monitoring year a mussel mound developed at both the platforms (longer-term effect) extending up to 30 m from pC, whereas similar soft-bottom communities were found at all the other distances. The geographical position plays an important role in the "timing" of the above effects. Moreover, despite the different environmental features, a 3-year monitoring plan can be effective to evaluate the potential impact on benthic communities of offshore gas platforms in the north-central Adriatic Sea.

Effect of Gd3+ on the colloidal stability of liposomes.

Lanthanide ions such as La3+ and Gd3+ are well known to have large effects on the structure of phospholipid membranes. Unilamellar vesicles of dipalmitoylphosphatidylcholine (DPPC) were prepared by sonication method and confirmed by transmission electron microscopy. The effects of concentration of gadolinium ions Gd3+ on DPPC unilamellar vesicles in aqueous media were studied by different techniques. As physical techniques, photon correlation spectroscopy, electrophoretic mobility, and differential scanning calorimetry were used. The theoretical predictions of the colloidal stability of liposomes were followed using the Derjaguin-Landau-Verwey-Overbeek theory. Changes in the size of liposomes and high polydispersities values were observed as Gd3+ concentration increases, suggesting that this cation induces the aggregation of vesicles. Electrophoretic mobility measurements on unilamellar vesicles as a function of Gd3+ ion concentration show that the vesicles adsorb Gd3+ ions. Above Gd3+ concentrations of 0.1 mol dm-3, the zeta potential and light scattering measurements indicate the beginning of aggregation process. For comparison with similar phospholipids, the zeta potential of phosphatidylcholine interacting with Gd3+ was measured, showing an analogous behavior. Differential scanning calorimetry has been used to determine the effect of Gd3+ on the transition temperature (Tc) and on the enthalpy (DeltaHc) associated with the process.