Optimization of the Elasticity and Adhesion of Catechol- or Dopamine-Loaded Gelatin Gels under Oxidative Conditions.

The synthesis of surgical adhesives is based on the need to design glues that give rise to strong and fast bonds without cytotoxic side effects. A recent trend in surgical adhesives is to use gel-forming polymers modified with catechol groups, which can undergo oxidative crosslinking reactions and are strongly adhesive to all kinds on surfaces in wet conditions. We previously showed that blending gelatin with catechol can yield strong adhesion when the catechol is oxidized by a strong oxidant. Our previous work was limited to the study of the variation in the sodium periodate concentration. In this article, for an in-depth approach to the interactions between the components of the gels, the influence of the gelatin, the sodium periodate and dopamine/(pyro)catechol concentration on the storage (G') and loss (G″) moduli of the gels, as well as their adhesion on steel, have been studied by shear rheometry. The hydrogels were characterized by infrared and UV-Vis spectroscopy and the size of their pores visualized by digital microscopy and SEM after freeze drying but without further additives. In terms of adhesion between two stainless steel plates, the optimum was obtained for a concentration of 10% w/v in gelatin, 10 mM in sodium periodate, and 20 mM in phenolic compounds. Below these values, it is likely that crosslinking has not been maximized and that the oxidizing environment is weakening the gelatin. Above these values, the loss in adhesiveness may result from the disruption of the alpha helixes due to the large number of phenolic compounds as well as the maintenance of an oxidizing environment. Overall, this investigation shows the possibility to design strongly adhesive hydrogels to metal surfaces by blending gelatin with polyphenols in oxidative conditions.

Polydopamine as a stable and functional nanomaterial.

The mussel inspired chemistry of dopamine leading to versatile coatings on the surface of all kinds of materials in a one pot process was considered as the unique aspect of catecholamine for a long time. Only recently, research has been undertaken to valorize the simultaneous oxidation and colloid formation in dopamine solutions in the presence of an oxidant. This mini review summarizes the synthesis methods allowing to get controlled nanomaterials, either nanoparticles, hollow capsules or nanotubes and even chiral nanomaterials from dopamine solutions. Finally the applications of those nanomaterials will be described.

Mimicking the Chemistry of Natural Eumelanin Synthesis: The KE Sequence in Polypeptides and in Proteins Allows for a Specific Control of Nanosized Functional Polydopamine Formation.

The oxidation of dopamine and of other catecholamines leads to the formation of conformal films on the surface of all known materials and to the formation of a precipitate in solution. In some cases, it has been shown that the addition of additives in the dopamine solution, like certain surfactants or polymers, polyelectrolytes, and certain proteins, allows to get polydopamine nanoparticles of controlled size and the concomitant decrease, in an additive/dopamine dependent manner, in film formation on the surface of the reaction beaker. However, the mechanism behind this controlled oxidation and self-assembly of catecholamines is not known. In this article, it is shown that a specific diad of amino acids in proteins, namely KE, allows for specific control in the oxidation-self-assembly of dopamine to obtain polydopamine@protein core-shell nanoparticles which are biocompatible. The interactions between dopamine and the adjacent KE amino acids potentially responsible for the size control of polydopamine aggregates was investigated by molecular dynamics simulations. The obtained core-shell nanoparticles display the biological activity of the protein used to control the self-assembly of PDA. The photon to heat conversion ability of PDA is conserved in the PDA@protein particles.

Enzymatically Active Polydopamine @ Alkaline Phosphatase Nanoparticles Produced by NaIO4 Oxidation of Dopamine.

Polydopamine (PDA) deposition, obtained from the oxidation of dopamine and other catecholamines, is a universal way to coat all known materials with a conformal coating which can subsequently be functionalized at will. The structural analogies between polydopamine and eumelanin, the black-brown pigment of the skin, were incited to produce stable polydopamine nanoparticles in solution, instead of amorphous precipitates obtained from the oxidation of dopamine. Herein, we demonstrate that size-controlled and colloidally stable PDA-based nanoparticles can be obtained in acidic conditions, where spontaneous auto-oxidation of dopamine is suppressed, using sodium periodate as the oxidant and a protein, like alkaline phosphatase (ALP), as a templating agent. The size of the PDA@ALP nanoparticles depends on the dopamine/enzyme ratio and the obtained particles display enzymatic activity of alkaline phosphatase, with an activity extending up to two weeks after particle synthesis. The PDA@ALP nanoparticles can be engineered in polyelectrolyte multilayered films to potentially design model biosensors.