Amino Acid and Oligopeptide Effects on Calcium Carbonate Solutions.

Biological organisms display sophisticated control of nucleation and crystallization of minerals. In order to mimic living systems, deciphering the mechanisms by which organic molecules control the formation of mineral phases from solution is a key step. We have used computer simulations to investigate the effects of the amino acids arginine, aspartic acid, and glycine on species that form in solutions of calcium carbonate (CaCO3) at lower and higher levels of supersaturation. This provides net positive, negative, and neutral additives. In addition, we have prepared simulations containing hexapeptides of the amino acids to consider the effect of additive size on the solution species. We find that additives have limited impact on the formation of extended, liquid-like CaCO3 networks in supersaturated solutions. Additives control the amount of (bi)carbonate in solution, but more importantly, they are able to stabilize these networks on the time scales of the simulations. This is achieved by coordinating the networks and assembled additive clusters in solutions. The association leads to subtle changes in the coordination of CaCO3 and reduced mobility of the cations. We find that the number of solute association sites and the size and topology of the additives are more important than their net charge. Our results help to understand why polymer additives are so effective at stabilizing dense liquid CaCO3 phases.

Complete inclusion of bioactive molecules and particles in polydimethylsiloxane: a straightforward process under mild conditions.

By applying a slow curing process, we show that biomolecules can be incorporated via a simple process as liquid stable phases inside a polydimethylsiloxane (PDMS) matrix. The process is carried out under mild conditions with regards to temperature, pH and relative humidity, and is thus suitable for application to biological entities. Fluorescence and enzymatic activity measurements show that the biochemical properties of the proteins and enzyme tested are preserved, without loss due to adsorption at the liquid-polymer interface. Protected from external stimuli by the PDMS matrix, these soft liquid composite materials are new tools of interest for robotics, microfluidics, diagnostics and chemical microreactors.

Prediction of Steam Burns Severity using Raman Spectroscopy on ex vivo Porcine Skin.

Skin burns due to accidental exposure to hot steam have often been reported to be more severe than the ones occurring from dry heat. While skin burns due to flames or radiant heat have been thoroughly characterized, the mechanisms leading to steam burns are not well understood and a conundrum still exists: can second degree burns occur without destruction of the epidermis, i.e. even before first degree burns are detected? Skin permeability is dependent both on temperature and on the kinetic energy of incoming water molecules. To investigate the mechanism underlying the injuries related to steam exposure, we used porcine skin as an ex vivo model. This model was exposed to either steam or dry heat before measuring the skin hydration via confocal Raman microspectroscopy. The results show that during the first minute of exposure to steam, the water content in both the epidermis and dermis increases. By analyzing different mechanisms of steam diffusion through the multiple skin layers, as well as the moisture-assisted bio-heat transfer, we provide a novel model explaining why steam burns can be more severe, and why steam can penetrate deeper and much faster than an equivalent dry heat.

Simulation of Calcium Phosphate Species in Aqueous Solution: Force Field Derivation.

A new force field has been derived for the aqueous calcium phosphate system that aims to reproduce the key thermodynamic properties of the system, including free energies of hydration of the ions and the solubility of the solid mineral phases. Interactions of three phosphate anions (PO43-, HPO42-, and H2PO4-) with water were calibrated through comparison with the results obtained from ab initio molecular dynamics using both GGA and hybrid density functional theory with dispersion corrections. In the solid state, the force field has been evaluated by benchmarking against experiment and other existing models and is shown to reproduce the structural and mechanical properties well, despite the primary focus being on thermodynamics. To validate the force field, the thermodynamics of ion pairing for calcium phosphate species in water has been computed and shown to be in excellent agreement with experimental data.