Auxetics and FEA: Modern Materials Driven by Modern Simulation Methods.

Auxetics are materials, metamaterials or structures which expand laterally in at least one cross-sectional plane when uniaxially stretched, that is, have a negative Poisson's ratio. Over these last decades, these systems have been studied through various methods, including simulations through finite elements analysis (FEA). This simulation tool is playing an increasingly significant role in the study of materials and structures as a result of the availability of more advanced and user-friendly commercially available software and higher computational power at more reachable costs. This review shows how, in the last three decades, FEA proved to be an essential key tool for studying auxetics, their properties, potential uses and applications. It focuses on the use of FEA in recent years for the design and optimisation of auxetic systems, for the simulation of how they behave when subjected to uniaxial stretching or compression, typically with a focus on identifying the deformation mechanism which leads to auxetic behaviour, and/or, for the simulation of their characteristics and behaviour under different circumstances such as impacts.

Progressive Local Accumulation of Self-Assembled Nanoreactors in a Hydrogel Matrix through Repetitive Injections of ATP.

Cellular functions are regulated with high spatial control through the local activation of chemical processes in a complex inhomogeneous matrix. The development of synthetic macroscopic systems with a similar capacity allows fundamental studies aimed at understanding the relationship between local molecular events and the emergence of functional properties at the macroscopic level. Here, we show that a kinetically stable inhomogeneous hydrogel matrix is spontaneously formed upon the local injection of ATP. Locally, ATP templates the self-assembly of amphiphiles into large nanoreactors with a much lower diffusion rate compared to unassembled amphiphiles. The local depletion of unassembled amphiphiles near the injection point installs a concentration gradient along which unassembled amphiphiles diffuse from the surroundings to the center. This allows for a progressive local accumulation of self-assembled nanoreactors in the matrix upon repetitive cycles of ATP injection separated by time intervals during which diffusion of unassembled amphiphiles takes place. Contrary to the homogeneous matrix containing the same components, in the inhomogeneous matrix the local upregulation of a chemical reaction occurs. Depending on the way the same amount of injected ATP is administered to the hydrogel matrix different macroscopic distributions of nanoreactors are obtained, which affect the location in the matrix where the chemical reaction is upregulated.

Time-gated fluorescence signalling under dissipative conditions.

Precise control over specific functions in the time domain is ubiquitous in biological systems. Here, we demonstrate time-gated fluorescence signalling under dissipative conditions exploiting an ATP-fueled self-assembly process. A temporal ATP-concentration gradient allows the system to pass through three states, among which only the intermediate state generates a fluorescent signal from a hydrophobic dye entrapped in the assemblies. The system can be reactivated by adding a new batch of ATP. The results indicate a strategy to rationally programme the temporal emergence of functions in complex chemical systems.

ATP-fuelled self-assembly to regulate chemical reactivity in the time domain.

Here, we exploit a small biomolecule - ATP - to gain temporal control over chemical reactivity in a synthetic system composed of small self-assembling molecules and reactants. The approach relies on the capacity of ATP to template the formation of amphiphile-based assemblies. The presence of the enzyme alkaline phosphatase causes a gradual decrease in the ATP-concentration in time and, consequently, a spontaneous dissociation of the assemblies. The uptake of apolar reactants in the hydrophobic domain of the assemblies leads to an enhancement of the reaction rate. It is shown that ATP-triggered self-assembly causes the selective upregulation of one out of two hydrazone-bond formation reactions that take place concurrently in the system. This leads to an inversion in the product ratio, which, however, is transient in nature because the upregulated reaction spontaneously reverts to its basal low reaction rate once the ATP has been consumed by the enzyme. Overall, the results demonstrate the potential of chemically-fuelled self-assembly under dissipative conditions to gain temporal control over reactivity in complex chemical systems.

Water-Soluble Colorimetric Amino[bis(ethanesulfonate)] Azobenzene pH Indicators: A UV-Vis Absorption, DFT, and 1H-15N NMR Spectroscopy Study.

Water-soluble azobenzene derivatives containing amino[bis(ethanesulfonate)] groups are demonstrated as colorful pH indicators in water and on filter paper. Vibrant color changes were observed from yellow/orange to pink between pH 1 and 4, which are attributed to an intramolecular charge-transfer mechanism. The pK as of the indicators range from 2.1 to 2.6. 1H/1H-15N NMR studies in deuterium oxide reveal that the protonation of the azobenzene pH indicators occurs predominantly at the ß-azo nitrogen atom, in agreement with the density functional theory calculations. Excellent selectivity for protons was confirmed in water over common biologically relevant metal ions. Studies in methanol, however, indicate that the pH indicator with a methoxy group ortho to the amino[bis(ethanesulfonate)] group facilitates the selective coordination of Cu2+ with a binding constant pßCu2+ of 4.6 ± 0.1. The indicators complement the existing library of azobenzene indicator dyes and may be useful for measuring the environmental pH at higher proton concentrations.

Acumulación de Zn en ovocitos de sapo Bufo arenarum: efecto sobre el metabolismo de carbohidratos / Accumulation of Zn in oocytes of Bufo arenarum frog: effect about the carboydrates metabolism

La exposición de hembras de sapo Buffo arerarum a aguas del río Reconquista (Provincia de Buenos Aires, Argentina) conduce a la acumulación de zinc (Zn) en sus ovarios. Las hembras tratadas de esta forma son capaces de ovular cuando son inyectadas con macerado de hipófisis, al igual que hembras controles. Los ovocitos obtenidos de hembras tratadas son capaces de fertilizar y desarrollar normalmente hasta el estadío de gástrula, mientras que presentan un 27 por ciento de inhibición del desarrollo embrionario a partir del estadío denominado respuesta muscular. In vivo la microinyección de Zn en ovocitos controles simultáneamente con [U-14C] Glucosa evidenció disminución en la síntesis de glucógeno y en la oxidación de la glucosa a través de la vía de las pentosas. La actividad de la enzima glucosa-6-fosfato deshidrogenasa en ausencia de agregado de Zn fue de 371,8 x 10 -3 U/ml.min. La enzima fue inhibida en vitro por el metal en forma dependiente de la concentración. Utilizando una concentración igual a 1,53mM de Zn, similar a la incorporada en ovario y a la microinyectada en los ensayos con glucosa radiactiva, se alcanzó un 62 por ciento de la máxima inhibición correspondiente a 3mM de Zn (248,7x10-3U/ml.min). Estos resultados concuerdan con un efecto inhibitorio del Zn sobre el desarrollo embrionario, mediado probablemente por una deficiente producción de NADPH, ribosa-5 fosfato y ATP en los ovocitos.