Insight on the deterioration of cultural objects: a multi-analytical approach to characterize degradation products of lead weights from a Steinway & sons piano.

The identification of the degradation products in objects of cultural significance, including musical instruments (e.g., a piano), is a key issue for the preservation and valorisation processes of cultural heritage. The aim of this study is to characterize the degradation products of lead weights from an important Steinway & sons piano using a multi-analytical approach that includes ionic chromatography (IC), X-ray diffraction (XRD) and Fourier transform-infrared (FTIR) spectroscopy analyses. These techniques allowed us to identify hydrocerussite as the main degradation product on the superficial layer of lead weights, followed by lead acetate and formate. Moreover, accelerated corrosion experiments in closed environments were performed under acetic and formic acid atmospheres to evaluate the development of lead acetate and formate over time. Exposure of lead weights to formic and acetic acid vapours leads to the prevalent formation of basic lead formate, which promotes the formation of hydrocerussite. These results can help to limit the degradation of these piano components and consequently preserve the sound of the piano itself.

Shape Deformation, Budding and Division of Giant Vesicles and Artificial Cells: A Review.

The understanding of the shape-change dynamics leading to the budding and division of artificial cells has gained much attention in the past few decades due to an increased interest in designing stimuli-responsive synthetic systems and minimal models of biological self-reproduction. In this respect, membranes and their composition play a fundamental role in many aspects related to the stability of the vesicles: permeability, elasticity, rigidity, tunability and response to external changes. In this review, we summarise recent experimental and theoretical work dealing with shape deformation and division of (giant) vesicles made of phospholipids and/or fatty acids membranes. Following a classic approach, we divide the strategies used to destabilise the membranes into two different types, physical (osmotic stress, temperature and light) and chemical (addition of amphiphiles, the addition of reactive molecules and pH changes) even though they often act in synergy when leading to a complete division process. Finally, we review the most important theoretical methods employed to describe the equilibrium shapes of giant vesicles and how they provide ways to explain and control the morphological changes leading from one equilibrium structure to another.

Collective Behavior of Urease pH Clocks in Nano- and Microvesicles Controlled by Fast Ammonia Transport.

The transmission of chemical signals via an extracellular solution plays a vital role in collective behavior in cellular biological systems and may be exploited in applications of lipid vesicles such as drug delivery. Here, we investigated chemical communication in synthetic micro- and nanovesicles containing urease in a solution of urea and acid. We combined experiments with simulations to demonstrate that the fast transport of ammonia to the external solution governs the pH-time profile and synchronizes the timing of the pH clock reaction in a heterogeneous population of vesicles. This study shows how the rate of production and emission of a small basic product controls pH changes in active vesicles with a distribution of sizes and enzyme amounts, which may be useful in bioreactor or healthcare applications.

Microplastics in the Environment: Intake through the Food Web, Human Exposure and Toxicological Effects.

Recently, studies on microplastics (MPs) have increased rapidly due to the growing awareness of the potential health risks related to their occurrence. The first part of this review is devoted to MP occurrence, distribution, and quantification. MPs can be transferred from the environment to humans mainly through inhalation, secondly from ingestion, and, to a lesser extent, through dermal contact. As regards food web contamination, we discuss the microplastic presence not only in the most investigated sources, such as seafood, drinking water, and salts, but also in other foods such as honey, sugar, milk, fruit, and meat (chickens, cows, and pigs). All literature data suggest not-negligible human exposure to MPs through the above-mentioned routes. Consequently, several research efforts have been devoted to assessing potential human health risks. Initially, toxicological studies were conducted with aquatic organisms and then with experimental mammal animal models and human cell cultures. In the latter case, toxicological effects were observed at high concentrations of MPs (polystyrene is the most common MP benchmark) for a short time. Further studies must be performed to assess the real consequences of MP contamination at low concentrations and prolonged exposure.

Effect of the Membrane Composition of Giant Unilamellar Vesicles on Their Budding Probability: A Trade-Off between Elasticity and Preferred Area Difference.

The budding and division of artificial cells engineered from vesicles and droplets have gained much attention in the past few decades due to an increased interest in designing stimuli-responsive synthetic systems. Proper control of the division process is one of the main challenges in the field of synthetic biology and, especially in the context of the origin of life studies, it would be helpful to look for the simplest chemical and physical processes likely at play in prebiotic conditions. Here we show that pH-sensitive giant unilamellar vesicles composed of mixed phospholipid/fatty acid membranes undergo a budding process, internally fuelled by the urea-urease enzymatic reaction, only for a given range of the membrane composition. A gentle interplay between the effects of the membrane composition on the elasticity and the preferred area difference of the bilayer is responsible for the existence of a narrow range of membrane composition yielding a high probability for budding of the vesicles.

Shape changes and budding of giant vesicles induced by an internal chemical trigger: an interplay between osmosis and pH change.

Shape transformation and budding of phospholipid/fatty acid giant hybrid vesicles can be induced by an internal chemical stimulus (pH change) when coupled with an osmotic shock. In particular, an autocatalytic enzymatic reaction set (urea-urease system), confined in the lumen of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC)/oleic acid (HOA) vesicles, can force the budding of the hosting vesicle, when properly fed by a trans-membrane substrate infusion. Herein, we elucidate the budding mechanism by simulating the shape changes of a vesicle during the enzymatic reaction. The area-difference-elasticity (ADE) theory is thus implemented to minimize the surface elastic energy and obtain the equilibrium shape at different values of the reduced volume and different values of the reduced preferred area difference (Δa0). Simulations, together with control experiments, unambiguously show that to obtain an effective vesicle shape transformation, the osmotic stress and the pH change in the lumen of the vesicle must act in synergy at the same timescale. Osmotic pressure induces a vesicle deflation (volume loss), while the pH change affects the preferred area difference between the outer and the inner membrane leaflets.

Hybrid giant lipid vesicles incorporating a PMMA-based copolymer.

BACKGROUND: In recent years, there has been a growing interest in the formation of copolymer-lipid hybrid self-assemblies, which allow combining and improving the main features of pure lipid-based and copolymer-based systems known for their potential applications in the biomedical field. As the most common method used to obtain giant vesicles is electroformation, most systems so far used low Tg polymers for their flexibility at room temperature. METHODS: Copolymers used in the hybrid vesicles have been synthesized by a modified version of the ATRP, namely the Activators ReGenerated by Electron Transfer ATRP and characterized by NMR and DSC. Giant hybrid vesicles have been obtained using electroformation and droplet transfer method. Confocal fluorescence microscopy was used to image the vesicles. RESULTS: Electroformation enabled to obtain hybrid vesicles in a narrow range of compositions (15 mol% was the maximum copolymer content). This range could be extended by the use of a droplet transfer method, which enabled obtaining hybrid vesicles incorporating a methacrylate-based polymer in a wide range of compositions. Proof of the hybrid composition was obtained by fluorescence microscopy using labeled lipids and copolymers. CONCLUSIONS: This work describes for the first time, to the best of our knowledge, the formation of giant hybrid polymer/lipid vesicles formed with such a content of a polymethylmethacrylate copolymer, the glass temperature of which is above room temperature. GENERAL SIGNIFICANCE: This work shows that polymer structures, more complex than the ones mostly employed, can be possibly included in giant hybrid vesicles by using the droplet transfer method. This will give easier access to functionalized and stimuli-responsive giant vesicles and to systems exhibiting a tunable permeability, these systems being relevant for biological and technological applications.

A Flavone-Based Solvatochromic Probe with A Low Expected Perturbation Impact on the Membrane Physical State.

The study of the cell membrane is an ambitious and arduous objective since its physical state is regulated by a series of processes that guarantee its regular functionality. Among the different methods of analysis, fluorescence spectroscopy is a technique of election, non-invasive, and easy to use. Besides, molecular dynamics analysis (MD) on model membranes provides useful information on the possibility of using a new probe, following its positioning in the membrane, and evaluating the possible perturbation of the double layer. In this work, we report the rational design and the synthesis of a new fluorescent solvatochromic probe and its characterization in model membranes. The probe consists of a fluorescent aromatic nucleus of a 3-hydroxyflavone moiety, provided with a saturated chain of 18 carbon atoms and a zwitterionic head so to facilitate the anchoring to the polar heads of the lipid bilayer and avoid the complete internalization. It was possible to study the behavior of the probe in GUV model membranes by MD analysis and fluorescence microscopy, demonstrating that the new probe can efficiently be incorporated in the lipid bilayer, and give a color response, thanks to is solvatochromic properties. Moreover, MD simulation of the probe in the membrane supports the hypothesis of a reduced perturbation of the membrane physical state.

Self-division of giant vesicles driven by an internal enzymatic reaction.

Self-division is one of the most common phenomena in living systems and one of the most important properties of life driven by internal mechanisms of cells. Design and engineering of synthetic cells from abiotic components can recreate a life-like function thus contributing to the understanding of the origin of life. Existing methods to induce the self-division of vesicles require external and non-autonomous triggers (temperature change and the addition of membrane precursors). Here we show that pH-responsive giant unilamellar vesicles on the micrometer scale can undergo self-division triggered by an internal autonomous chemical stimulus driven by an enzymatic (urea-urease) reaction coupled to a cross-membrane transport of the substrate, urea. The bilayer of the artificial cells is composed of a mixture of phospholipids (POPC, 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphatidylcholine) and oleic acid molecules. The enzymatic reaction increases the pH in the lumen of the vesicles, which concomitantly changes the protonation state of the oleic acid in the inner leaflet of the bilayer causing the removal of the membrane building blocks into the lumen of the vesicles thus decreasing the inner membrane area with respect to the outer one. This process coupled to the osmotic stress (responsible for the volume loss of the vesicles) leads to the division of a mother vesicle into two smaller daughter vesicles. These two processes must act in synergy; none of them alone can induce the division. Overall, our self-dividing system represents a step forward in the design and engineering of a complex autonomous model of synthetic cells.

Control of chemical chaos through medium viscosity in a batch ferroin-catalysed Belousov-Zhabotinsky reaction.

In this paper we show that the active interplay of nonlinear kinetics and transport phenomena in a chemical oscillator can be exploited to induce and control chaos. To this aim we use as a model system the ferroin-catalysed Belousov-Zhabotinsky (BZ) oscillating reaction, which is known to evolve to characteristic chaotic transient dynamics when carried out under batch and unstirred conditions. In particular, chemical chaos was found to appear and disappear by following a Ruelle-Takens-Newhouse (RTN) scenario. Here we use medium viscosity as a bifurcation parameter to tune the reaction-diffusion-convection (RDC) interplay and force the reaction in a specific sequence of dynamical regimes: either (i) periodic → quasi-periodic → chaotic or (ii) periodic → quasi-periodic or (iii) only periodic. The medium viscosity can be set by adding different amounts of surfactant (sodium dodecyl sulphate), known to have a little impact on the reaction mechanism, above its critical micelle concentration. Experimental results are supported by means of numerical simulations of a RDC model, which combines self-sustained oscillations to the related chemically-induced buoyancy convection.