Surface cleaning of artworks: structure and dynamics of nanostructured fluids confined in polymeric hydrogel networks.

Nanosystems and confinement tools for the controlled release of a cleaning agent, e.g., hydrogels and microemulsions, have been used for several years for the treatment of delicate surfaces in art restoration interventions. However, notwithstanding the unprecedented achievements from an application point of view, a fundamental comprehension of their interaction mechanism is still lacking. In this study PVA hydrogels, obtained via freeze-thaw processes, are prepared as scaffolds for water-based nanostructured fluids for application in the cleaning of artworks: rheological, thermal, microscopic and scattering techniques showed that, depending on the number of freeze-thaw cycles, the hydrogels exhibit different physicochemical and viscoelastic properties, making them suitable for application in a broad range of cleaning issues. The gels have been loaded with an oil-in-water microemulsion and the diffusion of the microemulsion droplets inside the polymeric network has been investigated through Fluorescence Correlation Spectroscopy (FCS), demonstrating that the microemulsion is permanently kept inside the matrix and can freely diffuse in the network. In addition, we show that when the gel-microemulsion system is put in contact with a layer of hydrophobic grime, a dynamic interaction between the microemulsion droplets and the underlying layer is established, leading to the solubilization of the hydrophobic molecules inside the droplets in the gel matrix. Thus, for the first time, through FCS, insights into the removal mechanism of hydrophobic grime upon interaction with a cleaning agent embedded in the polymeric matrix are obtained.

Influence of high energy electron irradiation on the network structure of gelatin hydrogels as investigated by small-angle X-ray scattering (SAXS).

The impact of high energy crosslinking on the network structure of gelatin hydrogels was investigated in comparison to physically entangled gels by small-angle X-ray scattering (SAXS). Physically entangled gelatin of increasing concentration exhibited a nearly constant correlation length of several nanometers. These gels had scattering behavior close to that of polymer coils swollen in a good solvent, as evidenced by the Porod exponent of 1.8. The mass fractal dimension decreased towards 1, indicating increased formation of semiflexible gelatin triple helices and rod-like structures as a function of the gelatin concentration. In contrast, electron irradiation lead to a decrease in the correlation length at doses above 20 kGy. Covalent crosslinking induced by electron irradiation lead to increased branching and formation of globular structures, as observed by a steady increase of both the Porod exponent and mass fractal dimension. Furthermore, the network mesh size systematically decreased from approximately 45 nm to under 20 nm with both additional physical and chemical crosslinking. These mesh sizes as obtained by SAXS were used to estimate the network shear modulus using several polymer models and were compared to macroscopic rheology measurements. Finally, SEM images of freeze-dried samples revealed changes in the microstructure of the irradiated hydrogels. Overall, fundamental differences in the network structures stemming from the crosslinking method were observed across a wide range of length scales.

Poly(ethylene glycol)-graft-poly(vinyl acetate) single-chain nanoparticles for the encapsulation of small molecules.

Amphiphilic poly(ethylene glycol)-graft-poly(vinyl acetate) copolymers with a low degree of grafting undergo self-folding in water driven by hydrophobic interactions, resulting in single-chain nanoparticles (SCNPs) possessing a hydrodynamic radius of about 10 nm. A temperature scan revealed a lower critical solution temperature (LCST)-type phase behavior. In addition, SAXS data collected close to the LCST showed that these SCNPs aggregate into one-dimensional elongated objects, preferentially. With respect to the typical linear complex-structured polymer chains, this material is ideally suited for industrial and/or biomedical applications because of its simple molecular architecture and persistence of SCNPs up to 100 mg mL-1. The so-obtained single-chain globular particles are able to swell upon loading with small hydrophobic molecules therefore promoting solubilization of flavors or drugs, which could be of interest in the food and pharmaceutical industry.

Aragonite crystals grown on bones by reaction of CO2 with nanostructured Ca(OH)2 in the presence of collagen. Implications in archaeology and paleontology.

The loss of mechanical properties affecting archeological or paleontological bones is often caused by demineralization processes that are similar to those driving the mechanisms leading to osteoporosis. One simple way to harden and to strengthen demineralized bone remains could be the in situ growth of CaCO3 crystals in the aragonite polymorph - metastable at atmospheric pressure -which is known to have very strong mechanical strength in comparison with the stable calcite. In the present study the controlled growth of aragonite crystals was achieved by reaction between atmospheric CO2 and calcium hydroxide nanoparticles in the presence of collagen within the deteriorated bones. In a few days the carbonation of Ca(OH)2 particles led to a mixture of calcite and aragonite, increasing the strength of the mineral network of the bone. Scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDS) and Fourier transform infrared (FT-IR) spectrometry showed that aragonite crystallization was achieved. The effect of the aragonite crystal formation on the mechanical properties of the deteriorated bones was investigated by means of X-rays microtomography, helium porosimetry, atomic force microscopy (AFM), and Vickers microhardness techniques. All these data enabled to conclude that the strength of the bones increased of a factor of 50-70% with respect to the untreated bone. These results could have immediate impact for preserving archeological and paleontological bone remains.

Formation and properties of amorphous magnesium-calcium phosphate particles in a simulated intestinal fluid.

HYPOTHESIS: The endogenous self-assembly of amorphous magnesium-calcium phosphate (AMCP) nanoparticles in human small intestine is an intriguing and newly-discovered process involved in immune-surveillance mechanisms. The study of nano and microparticles formation in complex media mimicking in vivo conditions contributes to unravel the features of endogenous AMCPs and, from a physico-chemical perspective, to shed light on the effect of biorelevant molecules on the precipitation of AMCPs. EXPERIMENTS: Endogenous-like AMCPs have been synthesized in a commercial simulated intestinal fluid (SIF), which contains biorelevant molecules such as lecithin and taurocholate. The properties of these particles were compared to the features of AMCPs synthesized in water. The stability of the amorphous phase as a function of time, as well as AMCPs' morphology, have been investigated. In particular, the effect of the organic molecules present in the SIF was examined in terms of incorporation in the nano and micro particles and on their nanoscale structure. FINDINGS: Taurocholate and lecithin, present in the SIF, enhance stability of amorphous phase against particles crystallization, and lead to the formation of smaller AMCP aggregates with a rougher surface. They are also incorporated in the inorganic phase, and their self-assembled structure leads to the formation of core-shell nanoparticles.

Associative properties of poly(ethylene glycol)-poly(vinyl acetate) comb-like graft copolymers in water.

The self-assembly of amphiphilic graft copolymers is generally reported for polymer melts or polymers deposited onto surfaces, while a small number of cases deal with binary mixtures with water. We report on the associative properties of poly(ethylene glycol)-graft-poly(vinyl acetate) (PEG-g-PVAc) comb-like copolymers in water, demonstrating the existence of a percolative behaviour when increasing the PEG-g-PVAc content. Rheology, light- and small-angle X-ray scattering experiments, together with dissipative particle dynamics simulations, reveal a progressive transition from spherical polymer single-chain nanoparticles (SCNPs) towards hierarchically complex structures as the weight fraction of the polymer in water increases. The ability of PEG-g-PVAc to attain different nano- and microstructures is of great importance in numerous applications such as in the fields of cosmetics, detergency and drug delivery.

Liquid-liquid phase separation of polymeric microdomains with tunable inner morphology: Mechanistic insights and applications.

HYPOTHESIS: Liquid-liquid phase separation (LLPS) can provide micron-sized liquid compartments dispersed in an aqueous medium. This phenomenon is increasingly appreciated in natural systems, e.g., in the formation of intracellular membraneless organelles, as well as in synthetic counterparts, such as complex coacervates and vesicles. However, the stability of these synthetic phase-separated microstructures versus coalescence is generally challenged by the presence of salts and/or surfactants, which narrows the range of possible applications. We propose a new strategy to obtain micron-sized liquid domains via LLPS, by mixing an amphiphilic copolymer with surfactants and sodium citrate in water at room temperature. EXPERIMENTS: Combining Confocal Laser Scanning Microscopy (CLSM) and Differential Scanning Calorimetry (DSC) with Dissipative Particle Dynamics (DPD) simulations, we map the phase diagram to detect LLPS and address the presence and morphology of these microscopic domains. This mapping in turn provides a first mechanistic hypothesis for the formation of such confined polymer-rich microenvironments. FINDINGS: LLPS is driven by the phase behavior of the copolymer in water and by its associative interactions with surfactants, combined with the water-sequestering ability of salting-out electrolytes. The key factor for LLPS and formation of microdomains is the entropy-driven dehydration of the copolymer head groups, which can be quantified through the Free Water Content (FWC). Interestingly, the internal morphology of the LLPS microdomains is finely controlled by the ratio between nonionic and anionic surfactants. Beside its applicative potential, this approach represents a tool for designing synthetic mimics that improve our understanding of the occurrence of LLPS in cells.

Poly(N-isopropylacrylamide)-hydroxyapatite nanocomposites as thermoresponsive filling materials on dentinal surface and tubules.

HYPOTHESIS: Dental decay, asa consequence of exposure to acidic foods and drinks, represents one of the most important tooth pathologies. Recently, enamel and dentinal surface remineralization using hydroxyapatite nano- and microparticles has been proposed; however, commercial remineralizing toothpastes are quite expensive, mostly due to the high costs of hydroxyapatite. Hence, we propose a thermoresponsive hybrid nanocomposite material as filler for tooth defects. The use of thermoresponsive composite particles aims at filling exposed dentinal tubules in response to a change of temperature in the oral cavity. In addition, the presence of the organic matrix contributes to the occlusion of the dentinal tubules, therefore reducing the needed amount of hydroxyapatite. EXPERIMENTS: Poly-N-isopropylacrylamide microgels containing different amounts of hydroxyapatite nanoparticles were prepared via radical polymerization in the presence of N-N'-methylenebisacrylamide as cross-linker followed by mechanical grinding. The nano- and microstructure of the hydrogels and their thermal behavior were studied via small-angle X-ray scattering (SAXS), scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). Defected teeth were treated with a dispersion of nanocomposite microparticles to simulate toothpaste action. FINDINGS: The hydrogels maintain their structure and thermal responsiveness when loaded with an amount of hydroxyapatite nanoparticles up to 2.3%w/w. In addition, the lower critical solution temperature is not affected by the presence of the mineral particles. Exposed dentinal tubules on the surface of test tooth samples were successfully occluded after 15 cycles of treatment with a dispersion of nanocomposite microparticles alternated with washing steps.

Enhanced formation of hydroxyapatites in gelatin/imogolite macroporous hydrogels.

HYPOTHESIS: Gelatin is widely investigated for the fabrication of synthetic scaffolds in bone tissue engineering. Practical limitations to its use are mainly due to the fast dissolution rate in physiological conditions and to the lack of pores with suitable dimensions for cell permeation. The aim of this work is to exploit imogolite clays as nucleation sites for the growth of calcium phosphates in gelatin-based hydrogels and to take advantage of a cryogenic treatment to obtain pores of ∼100µm. EXPERIMENTS: We evaluated the effect of imogolites and a biocompatible cross-linker on the gelatin network in terms of morphology, thermal and rheological behavior. The hydrogels were cryogenically-treated and characterized to investigate the modification of the polymer network, both at the micro- and nano-scale. The samples were mineralized to investigate the effect of imogolites on the formation of calcium phosphates. FINDINGS: The interaction between gelatin, imogolite and cross-linker leads to the modification of the hydrogel structure at the micro-scale, while minor effects are detected at the nano-scale. The cryogenic procedure is successful in generating pores with the desired size, while the presence of imogolites in the hydrogel promotes hydroxyapatites formation. These results demonstrate that imogolites can be effectively employed as functional fillers in polymer-based scaffolds.

Pluronic/gelatin composites for controlled release of actives.

This paper describes the preparation and the release properties of composite materials based on Pluronic F127 and gelatin hydrogels, which could be of interest in the field of enteral nutrition or drug administration. The composites were prepared by exploiting the opposite responsivity to temperature of a 20% w/w Pluronic F127 aqueous solution (critical gelation temperature around 23 °C) and gelatin (gel-sol temperature transition around 30 °C). Pluronic domains dispersed within a gelatin matrix were obtained by injecting cold Pluronic F127 solutions inside hot gelatin solutions, while homogenizing either with a magnetic stirrer or a high-energy mechanical disperser. Calorimetry indicates that the composites retain the individual gelling properties of Pluronic and gelatin. Different releasing properties were obtained as a function of the preparation protocol, the temperature and the pH. The release profiles have been studied by a Weibull analysis that clearly points out the dominating role of gelatin at 25 °C. At 37 °C the release accounts for a combined effect from both Pluronic F127 and gelatin, showing a more sustained profile with respect to gelatin hydrogels. This behavior, together with the ability of Pluronic F127 to upload both hydrophilic and hydrophobic drugs and flavors, makes these innovative composite materials very good candidates as FDA-approved carriers for enteral administration.