David Ruch

Self-assembly of tetramers of 5,6-dihydroxyindole explains the primary physical properties of eumelanin: experiment, simulation, and design.

Eumelanin is a ubiquitous pigment in nature and has many intriguing physicochemical properties, such as broad-band and monotonous absorption spectrum, antioxidant and free radical scavenging behavior, and strong nonradiative relaxation of photoexcited electronic states. These properties are highly related to its structural and mechanical properties and make eumelanin a fascinating candidate for the design of multifunctional nanomaterials. Here we report joint experimental-computational investigation of the structural and mechanical properties of eumelanin assemblies produced from dopamine, revealing that the mass density of dry eumelanin is 1.55 g/cm³ and its Youngs modulus is ≈5 GPa. We also find that wet eumelanin has a lower mass density and Youngs modulus depending on the water-to-melanin ratio. Most importantly, our data show that eumelanin molecules tend to form secondary structures based on noncovalent π stacking in both dry and wet conditions, with an interlayer distance between eumelanin molecules of 3.3 Å. Corresponding transmission electron microscope images confirm the supramolecular organization predicted in our simulations. Our simulations show that eumelanin is an isotropic material at a larger scale when eumelanin molecules are randomly oriented to form secondary structures. These results are in good agreement with experimental observations, density functional theory calculations, and bridge the gap between earlier experimental and small-scale quantum mechanical studies of eumelanin. We use the knowledge acquired from the simulations to select a partner molecule, a cationic phthalocyanine, allowing us to produce layer-by-layer films containing eumelanin that display an electrical conductivity 5 orders of magnitudes higher than that of pure eumelanin films.

Recent advances in high performance poly(lactide): from “green” plasticization to super-tough materials via (reactive) compounding

Due to its origin from renewable resources, its biodegradability, and recently, its industrial implementation at low costs, poly(lactide) (PLA) is considered as one of the most promising ecological, bio-sourced and biodegradable plastic materials to potentially and increasingly replace traditional petroleum derived polymers in many commodity and engineering applications. Beside its relatively high rigidity [high tensile strength and modulus compared with many common thermoplastics such as poly(ethylene terephthalate) (PET), high impact poly(styrene) (HIPS) and poly(propylene) (PP)], PLA suffers from an inherent brittleness, which can limit its applications especially where mechanical toughness such as plastic deformation at high impact rates or elongation is required. Therefore, the curve plotting stiffness vs. impact resistance and ductility must be shifted to higher values for PLA-based materials, while being preferably fully bio-based and biodegradable upon the application. This review aims to establish a state of the art focused on the recent progresses and preferably economically viable strategies developed in the literature for significantly improve the mechanical performances of PLA. A particular attention is given to plasticization as well as to impact resistance modification of PLA in the case of (reactive) blending PLA-based systems.

The reduction of Ag+ in metallic silver on pseudomelanin films allows for antibacterial activity but does not imply unpaired electrons

Dopamine-melanin films produced through the oxidation of dopamine in the presence of oxygen as an oxidant allow to reduce silver ions onto silver particles as already described in the paper by Lee et al. (H. Lee, S.M. Dellatore, W.M. Miller, P.B. Messersmith, Science 318 (2007) 426.). This reduction process has to occur through the oxidation of moieties present in the melanin film. This investigation shows that the free radicals present in the pseudomelanin film, quantified by means of electron spin resonance spectroscopy (ESR) for the first time, are not used in the transformation of Ag(+) cations to deposit silver. The ESR signal is hardly affected by the deposition of silver particles. On the other hand, X-ray photoelectron spectroscopy shows a small increase in the density of quinone groups and a small decrease of catechol groups on the surface of the film during the deposition of silver. This suggests that the deposited pseudomelanin films contain a significant fraction of catechol groups able to trigger reduction processes of metallic cations. These silver nanoparticles remain adherent to the melanin films and allow for a quantitative killing of Escherichia coli over a broad range of bacterial dilutions. However, the presence of the bacteria induces a release of the nanoparticles. The pseudomelanin films cannot be reused again for a silver ion reduction step. Nevertheless, the easy preparation of the pseudomelanin-silver composite and its effective one shot bacterial killing activity renders the strategy presented in this paper attractive. Some fundamental questions about redox process allowed by the pseudomelanin films will also be asked.

Excitonic effects from geometric order and disorder explain broadband optical absorption in eumelanin

Eumelanin is a ubiquitous biological pigment, and the origin of its broadband absorption spectrum has long been a topic of scientific debate. Here, we report a first-principles computational investigation to explain its broadband absorption feature. These computations are complemented by experimental results showing a broadening of the absorption spectra of dopamine solutions upon their oxidation. We consider a variety of eumelanin molecular structures supported by experiments or theoretical studies, and calculate the absorption spectra with proper account of the excitonic couplings based on the Frenkel exciton model. The interplay of geometric order and disorder of eumelanin aggregate structures broadens the absorption spectrum and gives rise to a relative enhancement of absorption intensity at the higher-energy end, proportional to the cube of absorption energy. These findings show that the geometric disorder model is as able as the chemical disorder model, and complements this model, to describe the optical properties of eumelanin.

Enhanced Adhesion over Aluminum Solid Substrates by Controlled Atmospheric Plasma Deposition of Amine-Rich Primers

Controlled chemical modification of aluminum surface is carried by atmospheric plasma polymerization of allylamine. The amine-rich coatings are characterized and tested for their behavior as adhesion promoter. The adhesion strength of aluminum-epoxy assemblies is shown to increase according to primary amino group content and coating thickness, which in turn can be regulated by plasma power parameters, allowing tailoring the coating chemical properties. The increase in adherence can be correlated to the total and primary amino group contents in the film, indicating covalent bonding of epoxy groups to the primer as the basis of the mechanical improvement.

Mechanistic investigation of a flame retardant coating made by layer-by-layer assembly

The efficiency of a flame retardant coating based on poly(allylamine) (PAH) and montmorillonite (MMT), deposited on polyamide 6 (PA6) bulk polymer was demonstrated in our previous work. In this paper we aim to investigate the mechanism of action of this flame retardant coating. To reach this objective, PA6-(PAH-MMT) at 40 bilayers was tested in a cone calorimeter and interrupted at different characteristic times: 25 s (after the fire test start), time to ignition, time of peak heat release rate and time of flameout. The condensed phases of the specimen residues obtained were characterized by scanning electron microscopy, X-ray diffraction, laser desorption ionization and solid state 13C nuclear magnetic resonance while the gas phase was evaluated by thermogravimetric analysis coupled with infrared spectroscopy and mass spectrometry. Finally the pyrolysis combustion flow calorimeter was used to evidence the effect of this layer-by-layer assembly in the gas phase. A possible mechanism explaining the improvement of the flame retardancy of a PA6 substrate in the presence of LbL coating made of PAH and clay is proposed.

Pressure and scattering regime influence on the EDS profile resolution at a composite interface in environmental SEM

Gas impact on the EDS profile resolution at the interface of composite interface resin/Al was investigated with two gaseous environments: helium and water vapor. Two main components of the global profile at the interface were investigated: the contrast of the profile and the spatial resolution. A complementary approach was developed by comparing gas nature impact versus the pressure and versus the scattering regime. The results show that the unscattered electron beam mainly governs EDS profile spatial resolution as long as the scattering regime is single or oligo scattering. Then for plural scattering, spatial resolution is dramatically degraded. In addition, the contrast is degraded since a gas is introduced, whatever the gas, the pressure and so the scattering regime. This approach would enable to better understand the respective contributions of the unscattered beam and the skirt and the influence of the gases nature on them.

Nano-ordered thin films achieved by soft atmospheric plasma polymerization

Plasma polymer thin films are of great interest in surface engineering in a wide range of applications. Herein, by using soft atmospheric plasma deposition parameters and by adapting these conditions to the used perfluorodecyl and dodecyl acrylates precursors, it is possible to get a high retention of monomer functionalities and a polymerization close to conventional methods. Molecular investigation revealed the presence of polymeric moieties and the mechanism of plasma polymerization has been mainly based on the polymerization by activation of the ethylenic groups. X-ray diffraction analyses have shown the presence of a smectic lamellar where the polyacrylate backbone was the amorphous phase and fluorinated and alkyl side chains were the hexagonal crystalline section. Wetting properties have been evaluated and finally showed hydrophobic surfaces

Skirting effects in the variable pressure scanning electron microscope: limitations and improvements.

A new approach has been initiated to improve the spatial lateral resolution of the X-ray microanalysis and the backscattered electrons modes in variable pressure or environmental scanning electron microscope (VP-ESEM). This approach is based on correlation between two concepts: the electron beam skirt radius in the gas (R(S)) and the generation volume radius (R(X)) of X-ray signals and the generation volume radius (R(BSE)) of backscattered electrons in the material. In order to follow the relationship between R(S), R(X) and R(BSE), PMMA polymer, silicon oxide and aluminium are used. The results of the simulation show the existence of the best lateral resolution conditions named R (P, E) depending on the pressure and the energy for each material. This approach will enable us to propose some optimal experimental conditions to characterize different materials.

Influence of the nature of the polycation on the adsorption kinetics and on exchange processes in polyelectrolyte multilayer films.

The deposition of polyelectrolyte multilayer films (PEMs) appears more and more as a versatile tool to functionalize a broad range of materials with coatings having controlled thicknesses and properties. To increase the control over the properties of such coatings, a good knowledge of their deposition mechanism is required. Since Cohen Stuart et al. (Langmuir 18 (2002) 5607-5612) showed that the adsorption of one polyelectrolyte could induce desorption of polyelectrolyte complexes instead of regular deposition, more and more findings highlight peculiarities in the deposition of such films. Herein we demonstrate that the association of sodium polyphosphate (PSP) as the polyanion and either poly(-L-lysine hydrobromide) (PLL) or poly(allylamine chloride) (PAH) as the polycations may lead to non-monotonous film deposition as a function of time. Complementary, films containing PSP and PLL can be obtained from a (PLL-HA)(n) template films after the exchange of HA (hyaluronic acid) from the sacrificial template by PSP from the solution. This exchange is accompanied by pronounced film erosion. However, when starting from a (PAH-HA)(n) template, the film erosion and exchange due to the contact with PSP is by far less pronounced, nevertheless the film morphology changes. These findings show that the nature of the polycation used to deposit the PEM film may have a profound influence of the films response to a competing polyanion.