Direct observation of the effects of chemical fixation in MNT-1 cells: A SE-ADM and Raman study.

Aldehydes fixation was accidentally discovered in the early 20th century and soon became a widely adopted practice in the histological field, due to an excellent staining enhancement in tissues imaging. However, the fixation process itself entails cell proteins denaturation and crosslinking. The possible presence of artifacts, that depends on the specific system under observation, must therefore be considered to avoid data misinterpretation. This contribution takes advantage of scanning electron assisted-dielectric microscopy (SE-ADM) and Raman 2D imaging to reveal the possible presence and the nature of artifacts in unstained, and paraformldehyde, PFA, fixed MNT-1 cells. The high resolution of the innovative SE-ADM technique allowed the identification of globular protein clusters in the cell cytoplasm, formed after protein denaturation and crosslinking. Concurrently, SE-ADM images showed a preferential melanosome adsorption on the cluster's outer surface. The micron-sized aggregates were discernible in Raman 2D images, as the melanosomes signal, extracted through 2D principal component analysis, unequivocally mapped their location and distribution within the cells, appearing randomly distributed in the cytoplasm. Protein clusters were not observed in living MNT-1 cells. In this case, mature melanosomes accumulate preferentially at the cell periphery and are more closely packed than in fixed cells. Our results show that, although PFA does not affect the melanin structure, it disrupts melanosome distribution within the cells. Proteins secondary structure, conversely, is partially lost, as shown by the Raman signals related to α-helix, ß-sheets, and specific amino acids that significantly decrease after the PFA treatment.

Hierarchical Emulsion Structure and Functionality Regulated by Coexisting Bicontinuous Microemulsion and Liquid Crystal Domains.

Since microemulsions are usually low viscosity fluids, enhanced rheological properties while maintaining their structure-derived functionality have long been desired from an industrial application point of view. However, for instance, it is practically difficult to thicken bicontinuous microemulsions (BCMEs) without perturbing their alternating domain structure or to emulsify oils using BCME having ultralow interfacial tension as an external phase. In this study, a methodology called a BCLC emulsification technique has been constructed to obtain oil-in-water emulsions stabilized by coexisting BCME and liquid crystal (LC) phases. The produced emulsions based on polyglyceryl-10 diisostearate, polyglyceryl-6 dicaprate, cetyl ethylhexanoate, and water are structurally scrutinized by means of small- and wide-angle X-ray scattering (SWAXS), freeze fracture transmission electron microscopy (FF-TEM), and scanning electron assisted dielectric microscopy (SE-ADM). The data provide experimental evidence that this methodology enables one to control the bending elasticity of the interfacial membranes and consequent long-range order of the BCME domains. Moreover, closely correlated with the interfacial membrane properties, submicrometer-sized fine oil droplets are supported by the LC networks and agglomerated into spongy or network-like phase-separation patterns. The resulting nonfluidic, jelly emulsions are particularly useful in cosmetics because of combined BCME-derived high cleansing performance and excellent usability owing to the enhanced viscosity. The thickening mechanisms are essentially different from those of common lamellar-gel-stabilized oil-in-water emulsions, which utilize crystalline lamellar gel networks as oil droplet stabilizers.

From Nanoparticles to Gels: A Breakthrough in Art Conservation Science.

Cultural heritage is a crucial resource to increase our society's resilience. However, degradation processes, enhanced by environmental and anthropic risks, inevitably affect works of art, hindering their accessibility and socioeconomic value. In response, interfacial and colloidal chemistry has proposed valuable solutions over the past decades, overcoming the limitations of traditional restoration materials and granting cost- and time-effective remedial conservation of the endangered artifacts. Ranging from inorganic nanoparticles to hybrid composites and soft condensed matter (gels, microemulsions), a wide palette of colloidal systems has been made available to conservators worldwide, targeting the consolidation, cleaning, and protection of works of art. The effectiveness and versatility of the proposed solutions allow the safe and effective treatment of masterpieces belonging to different cultural and artistic productions, spanning from classic ages to the Renaissance and modern/contemporary art. Despite these advancements, the formulation of materials for the preservation of cultural heritage is still an open, exciting field, where recent requirements include coping with the imperatives of the Green Deal to foster the production of sustainable, low-toxicity, and environmentally friendly systems. This review gives a critical overview starting from pioneering works up to the latest advancements in colloidal systems for art conservation, a challenging topic where effective solutions can be transversal to multiple sectors even beyond cultural heritage preservation, from the pharmaceutical and food industry, to cosmetics, tissue engineering, and detergency.

Twin-chain polymer hydrogels based on poly(vinyl alcohol) as new advanced tool for the cleaning of modern and contemporary art.

Conservation of our cultural heritage is fundamental for conveying to future generations our culture, traditions, and ways of thinking and behaving. Cleaning art, in particular modern/contemporary paintings, with traditional tools could be risky and impractical, particularly on large collections of important works to be transferred to future generations. We report on advanced cleaning systems, based on twin-chain polymer networks made of poly(vinyl alcohol) (PVA) chains, semiinterpenetrated (semi-IPN) with PVA of lower molecular weight (L-PVA). Interpenetrating L-PVA causes a change from gels with oriented channels to sponge-like semi-IPNs with disordered interconnected pores, conferring different gel (and solvent) dynamics. These features grant residue-free, time efficient cleaning capacity and effective dirt capture, defeating risks for the artifact, making possible a safer treatment of important collections, unconceivable with conventional methods. We report as an example the conservation of Jackson Pollock's masterpieces, cleaned in a controlled way, safety and selectivity with unprecedented performance.

How Science Can Contribute to the Remedial Conservation of Cultural Heritage.

Colloid science is contributing solutions to counteract the degradation of artifacts, favoring their transfer to future generations. Advanced materials such as nanoparticles, coatings, gels and microemulsions have been assessed in conservation, spanning from archeological sites to modern and contemporary art. We give an overview of the fundamental milestones and latest innovations in conservation science, targeting solutions and tools for remedial conservation based on green nanomaterials and hybrid systems. Future perspectives and outstanding challenges in this exciting field are then outlined.

Functionalised nanoclays as microstructure modifiers for calcium and magnesium silicate hydrates.

Calcium silicate hydrate (C-S-H) is the main binding product of ordinary Portland concrete (OPC). Unfortunately, OPC production generates ∼5% of all anthropomorphic CO2. Among the most promising green alternatives, magnesium silicate hydrate (M-S-H) is a colloidal gel equivalent to C-S-H which exhibits weaker mechanical properties. Here we investigated the effect of the inclusion of aluminosilicate nanoclays (HNTs) on the microstructure of the silicate hydrate gels as a strategy to ultimately improve their mechanical properties. The microstructure of C-S-H and M-S-H gels synthesized with and without carboxylic or polycarboxylic functionalised HNTs (HNT-COOH, HNT-PAA) was investigated by a multi-technique approach including small- and wide-angle X-ray scattering (SWAXS) and scanning electron microscopy (SEM). The results indicate that, during C-S-H formation in solution, HNTs decrease the size of the disk-like globules with little influence on the spacing of calcium silicate layers. In the case of M-S-H, the presence of functionalised HNTs has a reduced effect on the hydrate structure as a result of the weaker interaction of the carboxylic moieties with Mg2+ ions. SEM investigation on the synthesized composites shows that HNT-PAA are better included in the hydration products. Moreover, in the proximity of the PAA functionalised surfaces, less extended aggregates are formed. The morphology at the micron scale for M-S-H and C-S-H with HNT-COOH is conserved.

Restoration of paper artworks with microemulsions confined in hydrogels for safe and efficient removal of adhesive tapes.

The presence of pressure-sensitive tapes (PSTs) on paper artworks, either fortuitous or specifically applied for conservation purposes, is one of the most frequent and difficult issues encountered during restoration. Aged PSTs can damage or disfigure artworks, compromising structural integrity, readability, and enjoyment. Current procedures are often inherently hazardous for artistic media and paper support. Challenged by the necessity to remove PSTs from a contemporary and an ancient drawing (20th century, by artists da Silva and Hayter, and a 16th-century drawing of one figure from the Sistine Chapel by Michelangelo), we addressed this issue from a physicochemical perspective, leveraging colloid and interface science. After a characterization of the specific PSTs present on the artifact, we selected a highly water-retentive hydrogel as the host of 23% wt/wt of "green" organic solvents uniformly dispersed within the gel in the form of nanosized droplets. The double confinement of the organic solvent in the nanodroplets and into the gel network promotes a tailored, controlled removal of PSTs of different natures, with virtually no interaction with the solvent-sensitive artwork. This noninvasive procedure allows complete retrieval of artwork readability. For instance, in the ancient drawing, the PST totally concealed the inscription, "di mano di Michelangelo" ("from Michelangelo's hand"), a possibly false attribution hidden by a collector, which is now perfectly visible and whose origin is currently under investigation. Remarkably, the same methodology was successful for the removal of aged PST adhesive penetrated inside paper fibers of a drawing from the celebrated artist Lucio Fontana.

Advanced Materials in Cultural Heritage Conservation.

Cultural Heritage is a crucial socioeconomic resource; yet, recurring degradation processes endanger its preservation. Serendipitous approaches in restoration practice need to be replaced by systematically addressing conservation issues through the development of advanced materials for the preservation of the artifacts. In the last few decades, materials and colloid science have provided valid solutions to counteract degradation, and we report here the main highlights in the formulation and application of materials and methodologies for the cleaning, protection and consolidation of works of art. Several types of artifacts are addressed, from murals to canvas paintings, metal objects, and paper artworks, comprising both classic and modern/contemporary art. Systems, such as nanoparticles, gels, nanostructured cleaning fluids, composites, and other functional materials, are reviewed. Future perspectives are also commented, outlining open issues and trends in this challenging and exciting field.

Rational Design of Sustainable Liquid Microcapsules for Spontaneous Fragrance Encapsulation.

The high volatility, water-immiscibility, and light/oxygen-sensitivity of most aroma compounds represent a challenge to their incorporation in liquid consumer products. Current encapsulation methods entail the use of petroleum-based materials, initiators, and crosslinkers as well as mixing, heating, and purification steps. Hence, more efficient and eco-friendly approaches to encapsulation must be sought. Herein, we propose a simple method by making use of a pre-formed amphiphilic polymer and employing the Hansen Solubility Parameters approach to determine which fragrances could be encapsulated by spontaneous coacervation in water. The coacervates do not precipitate as solids but they remain suspended as colloidally stable liquid microcapsules, as demonstrated by fluorescence correlation spectroscopy. The effective encapsulation of fragrance is proven through confocal Raman spectroscopy, while the structure of the capsules is investigated by means of cryo FIB/SEM, confocal laser scanning microscopy, and small-angle X-ray scattering.

Spotting aged dyes on paper with SERS.

Surface enhanced Raman spectroscopy (SERS) is a highly sensitive technique for the non- or minimally invasive identification of molecules at very low concentrations. In this work, SERS is exploited using naked laser-ablated gold nanoparticles (AuNPs) for the detection of dyes on artificially aged paper inked with a ballpoint pen. Although several studies on inks with SERS are present in the literature, most of them report on the investigations on freshly prepared products, and less information is present on the detection of aged dyes and inks using SERS. Ballpoint inks are commonly used in daily activities, but have also been employed by several contemporary artists. These inks are very sensitive to light, and they discolor rapidly, making their detection demanding. In the present work, the SERS spectra of a ballpoint pen ink on two types of paper were analyzed after light-induced ageing, and the importance of the dye-AuNP interaction is discussed. The results show that the interpretation of the SERS spectra of the aged samples, such as those of interest in the Cultural Heritage field, is a tricky and delicate operation and that the diffusion of the dyes to the hot spot regions of the plasmonic nanoparticles plays a pivotal role in the detection of degraded ink components. Therefore, appropriate evaluation of the factors affecting the molecule-plasmonic nanoparticle interactions and of the history of the artwork to be analyzed is fundamental to avoiding the misinterpretation of the spectra and, consequently, of the original composition of the analyzed artwork.

Energy landscape in protein folding and unfolding.

We use (1)H NMR to probe the energy landscape in the protein folding and unfolding process. Using the scheme ⇄ reversible unfolded (intermediate) → irreversible unfolded (denatured) state, we study the thermal denaturation of hydrated lysozyme that occurs when the temperature is increased. Using thermal cycles in the range 295 < T < 365 K and following different trajectories along the protein energy surface, we observe that the hydrophilic (the amide NH) and hydrophobic (methyl CH3 and methine CH) peptide groups evolve and exhibit different behaviors. We also discuss the role of water and hydrogen bonding in the protein configurational stability.

Nonaqueous Microemulsion in the Bmim Tf2N/Brij 30/ n-Nonane System: Structural Investigation and Application as Gold Nanoparticle Microreactor.

Microemulsions based on ionic liquids (ILs) are being increasingly studied in many different areas of physical chemistry because of the attractive properties of ILs. In particular, waterless microemulsions where the IL represents the polar phase can be of interest for those applications that demand the nanosegregation of polar substances, but in which the absence of water is a strict requirement. In this work, we prepared a reverse, nonaqueous microemulsion based on the low-viscosity room-temperature IL, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide , the surfactant Brij 30, and n-nonane. The systems were characterized by dynamic light scattering and small-angle X-ray scattering; the IL/oil microemulsion was further employed as a templating system for the synthesis of gold nanoparticles from hydrogen tetrachloroaurate(III), HAuCl4, by UV-photoreduction technique.

Water as a Probe of the Colloidal Properties of Cement.

Cement is produced by mixing mineral phases based on calcium silicates and aluminates with water. The hydration reaction of the mixture leads to a synthetic material with outstanding properties that can be used as a binder for construction applications. Despite the importance of cement in society, for a long time, the chemical reactions involved in its hydration remained poorly understood as a result of the complexity of hydration processes, nanostructure, and transport phenomena. This feature article reviews the recently obtained results using water as a probe to detail the essential features in the setting process. By examining the peculiar physicochemical properties of water, fundamental information on the evolving inorganic colloid matrix can be deduced, ranging from the fractal nanostructure of the inorganic silicate framework to the transport phenomena inside the developing porosity. A similar approach can be transferred to the investigation of a plethora of other complex systems, where water plays the main role in determining the final structural and transport properties (i.e., biomaterials, hydrogels, and colloids).

Microemulsions, Micelles, and Functional Gels: How Colloids and Soft Matter Preserve Works of Art.

Colloid science provides fundamental knowledge to fields such as the pharmaceutical, detergency, paint, and food industry. An exciting application is art conservation, which poses a challenge owing to the complex range of interfacial interactions involved in restoring artefacts. Currently, the majority of the most performing and environmentally safe cleaning and consolidation agents for artworks belong to soft matter and colloids. The development and application of increasingly complex systems, from microemulsions to semi-interpenetrating hydrogels containing such fluids, is presented. These systems have been used on diverse artefacts, from Renaissance frescos to works by Picasso and Pollock. Chemical design can be implemented to meet the requirements of curators, and knowledge of the colloid structure and dynamics can overcome serendipitous approaches of traditional conservation practice. Future perspectives for soft matter and colloid science in the field of cultural heritage preservation are also summarized.

Polymer Film Dewetting by Water/Surfactant/Good-Solvent Mixtures: A Mechanistic Insight and Its Implications for the Conservation of Cultural Heritage.

Aqueous nanostructured fluids (NSFs) have been proposed to remove polymer coatings from the surface of works of art; this process usually involves film dewetting. The NSF cleaning mechanism was studied using several techniques that were employed to obtain mechanistic insight on the interaction of a methacrylic/acrylic copolymer (Paraloid B72) film laid on glass surfaces and several NSFs, based on two solvents and two surfactants. The experimental results provide a detailed picture of the dewetting process. The gyration radius and the reduction of the Tg of Paraloid B72 fully swollen in the two solvents is larger for propylene carbonate than for methyl ethyl ketone, suggesting higher mobility of polymer chains for the former, while a nonionic alcohol ethoxylate surfactant was more effective than sodium dodecylsulfate in favoring the dewetting process. FTIR 2D imaging showed that the dewetting patterns observed on model samples are also present on polymer-coated mortar tiles when exposed to NSFs.

Probing the Cleaning of Polymeric Coatings by Nanostructured Fluids: A QCM-D Study.

Complex fluids composed of water, an organic solvent, and a surfactant have been recently employed as cleaning systems to remove hydrophobic materials, such as polymeric coatings, from solid surfaces. The simultaneous presence of surfactants and an organic solvent with good affinity for the polymer was proven necessary for the polymer's removal, but the comprehension of the cleaning mechanism is poorly understood. In this Article, we investigated the mechanism of removal, highlighting the specific role of each component in the interaction with the polymer film. In particular, the results from quartz crystal microbalance with dissipation monitoring (QCM-D) were compared with those obtained by using confocal microscopy to follow in situ the effect of a nanostructured fluid, i.e., a ternary formulation containing water, 2-butanone (MEK) as a good solvent for the polymer, and a nonionic surfactant (C9-11 ethoxylated alcohol, BR) on acrylic copolymer films (Paraloid B72). The results indicate a two-step process: (i) the penetration of the good solvent across the film causes the swelling of the polymer, the weakening of polymer-polymer interactions, and an increase of molecular mobility, followed by (ii) the slow adsorption of amphiphilic aggregates promoting the film detachment from the solid substrate. A different behavior is observed in the presence of similar formulations containing an anionic surfactant (sodium dodecyl sulfate, SDS), where the adsorption of SDS micelles on the surface of the polymeric film hinders solvent access into the polymer layer, rather than promoting its detachment from the solid substrate.

Adsorption of Amino Acids and Glutamic Acid-Based Surfactants on Imogolite Clays.

Aluminum oxide surfaces are of utmost interest in different biotech applications, in particular for their use as adjuvants (i.e., booster of the immune response against infectious agents in vaccines production). In this framework, imogolite clays combine the chemical flexibility of an exposed alumina surface with 1D nanostructure. This work reports on the interaction between amino acids and imogolite, using turbidimetry, ζ-potential measurements, and Fourier transform infrared spectroscopy as main characterization tools. Amino acids with different side chain functional groups were investigated, showing that glutamic acid (Glu) has the strongest affinity for the imogolite surface. This was exploited to prepare a composite material made of a synthetic surfactant bearing a Glu polar head and a hydrophobic C12 alkyl tail, adsorbed onto the surface of imogolite. The adsorption of a model drug (rhodamine B isothiocyanate) by the hybrid was evaluated both in water and in physiological saline conditions. The findings of this paper suggest that the combination between the glutamate headgroup and imogolite represents a promising platform for the fabrication of hybrid nanostructures with tailored functionalities.

Nanofluids and chemical highly retentive hydrogels for controlled and selective removal of overpaintings and undesired graffiti from street art.

One of the main problems connected to the conservation of street art is the selective removal of overlying undesired graffiti, i.e., drawings and tags. Unfortunately, selective and controlled removal of graffiti and overpaintings from street art is almost unachievable using traditional methodologies. Recently, the use of nanofluids confined in highly retentive pHEMA/PVP semi-interpenetrated polymer networks was proposed. Here, we report on the selective removal of acrylic overpaintings from a layer of acrylic paint on mortar mockups in laboratory tests. The results of the cleaning tests were characterized by visual and photographic observation, optical microscopy, and FT-IR microreflectance investigation. It was shown that this methodology represents a major advancement with respect to the use of nonconfined neat solvents.