Josep Sedó

Catechol-based biomimetic functional materials

Catechols are found in nature taking part in a remarkably broad scope of biochemical processes and functions. Though not exclusively, such versatility may be traced back to several properties uniquely found together in the o-dihydroxyaryl chemical function; namely, its ability to establish reversible equilibria at moderate redox potentials and pHs and to irreversibly cross-link through complex oxidation mechanisms; its excellent chelating properties, greatly exemplified by, but by no means exclusive, to the binding of Fe(3+); and the diverse modes of interaction of the vicinal hydroxyl groups with all kinds of surfaces of remarkably different chemical and physical nature. Thanks to this diversity, catechols can be found either as simple molecular systems, forming part of supramolacular structures, coordinated to different metal ions or as macromolecules mostly arising from polymerization mechanisms through covalent bonds. Such versatility has allowed catechols to participate in several natural processes and functions that range from the adhesive properties of marine organisms to the storage of some transition metal ions. As a result of such an astonishing range of functionalities, catechol-based systems have in recent years been subject to intense research, aimed at mimicking these natural systems in order to develop new functional materials and coatings. A comprehensive review of these studies is discussed in this paper.

Versatile Nanostructured Materials via Direct Reaction of Functionalized Catechols

A facile one-step polymerization strategy is explored to achieve novel catechol-based materials. Depending on the functionality of the catechol, the as-prepared product can be used to modify at will the surface tension of nano and bulk structures, from oleo-/hydrophobic to highly hydrophilic. A hydrophobic catechol prepared thus polymerized shows the ability to self-assemble as solid nanoparticles with sticky properties in polar solvent media. Such a versatile concept is ideal for the development of catechol-based multifunctional materials.

Mussel-Inspired Hydrophobic Coatings for Water-Repellent Textiles and Oil Removal

A series of catechol derivatives with a different number of linear alkyl chain substituents, and different length, have been shown to polymerize in the presence of aqueous ammonia and air, yielding hydrophobic coatings that present the ability to provide robust and efficient water repellency on weaved textiles, including hydrophilic cotton. The polymerization strategy presented exemplifies an alternative route to established melanin- and polydopamine-like functional coatings, affording designs in which all catechol (adhesive) moieties support specific functional side chains for maximization of the desired (hydrophobic) functionality. The coatings obtained proved effective in the transformation of polyester and cotton weaves, as well as filter paper, into reusable water-repellent, oil-absorbent materials capable of retaining roughly double their weight in model compounds (n-tetradecane and olive oil), as well as of separating water/oil mixtures by simple filtration.

Crystal Structures of Chiral Diastereoisomers of a Carbon-Based High-Spin Molecule

A chiral organic compound that displays magnetic properties has been synthesized for the first time. Two diastereomers of a molecule having an S=3/2 spin state have been characterized by X-ray crystal structure analysis (one of the diastereomers is shown in the space-filling model on the right). Optical resolution of one pair of stereoisomers was possible by chiral stationary phase HPLC.

Temperature‐Controlled Switchable Photochromism in Solid Materials

A novel strategy to achieve thermally switchable photochromism in solid materials is reported, which relies on the preparation of polymeric core-shell capsules containing solutions of photochromic dyes in acidic phase-change materials. Upon changing the phase (solid or liquid) of the encapsulated medium, one of the two photochromic states of the system is selectively stabilized on demand, allowing for reversible interconversion between direct and reverse photochromism when thermally scanning through the melting temperature of the phase-change material. This strategy, which does not require the addition of external agents or chemical modification of the dyes, proved to be general for different spiropyran photochromes and to be applicable to the fabrication of a variety of functional materials by simply embedding the capsules obtained into a solid matrix of choice.

Influence of the Molecular Surface Characteristics of the Diastereoisomers of a Quartet Molecule on their Physicochemical Properties: A Linear Solvation Free-Energy Study

The difference in ability of a quartet molecule to interact with the neighboring solvent molecules is influenced by the molecular surface characteristics of the two diastereomers of the molecule. Therefore, molecular parameters like the surface area and the fractal dimension (see figure) control some of their physicochemical properties, such as their differential chromatographic retention of these two diastereomers, their isomerization equilibrium, and tumbling processes in solid or viscous amorphous matrices.

Biocompatible polydopamine-like particles for the removal of heavy metals at extremely low concentrations

A family of catechol-based submicron particles, with sizes between 200 and 300 nm, was tested for the removal of Cd(II), Pb(II) and Cr(VI) in water. The highest adsorption capacity was obtained with catecholbased particles in the case of Pb(II), followed by Cd(II). However, the catechol particles failed to adsorb Cr(VI). Our results indicate an up to four-fold increase of the adsorption capacity of these particles compared to that of activated carbon under the same experimental conditions. To check the biocompatible character of the submicron particles, their stability was evaluated in a phosphate buffer solution (PBS) and in a cell culture medium. The results confirmed that the presence of proteins in the medium favors their stability. A bioluminescent Vibrio fischeri test and a cytotoxicity assay on the HepG2 cell line were used to determine that the catechol particles did not exhibit any substantial toxicity. The results show that these catechol-based particles can be used as an efficient biocompatible adsorbent to remove heavy metals at extremely low concentrations.

Study of intervalence bands due to reversible intramolecular electron transfer phenomena in purely organic mixed-valence high-spin molecules

Abstract Up to now, few examples of reversible electron intramolecular transfer phenomena in purely organic mixed-valence molecules have been studied in detail. We present the first example of a purely organic molecule in which, in addition to the observation of an optical electron transfer between open-shell and anionic sites, two radical centers remain ferromagnetic ally coupled inside the molecule. The intervalence band which arises from the optical ET is clearly observed in the far NIR range and is quantitatively analyzed by means of an ad hoc model. Since these properties are rather unusual for purely organic compounds, even separately, this and similar molecules offer us a unique chance for studying the reciprocal influence between electron transfer and strong magnetic coupling in organic systems.

Copolymerization of a Catechol and a Diamine as a Versatile Polydopamine-Like Platform for Surface Functionalization: The Case of a Hydrophobic Coating

The covalent functionalization of surfaces with molecules capable of providing new properties to the treated substrate, such as hydrophobicity or bioactivity, has been attracting a lot of interest in the last decades. For achieving this goal, the generation of a universally functionalizable primer coating in one-pot reaction and under relatively mild conditions is especially attractive due to its potential versatility and ease of application. The aim of the present work is to obtain such a functionalizable coating by a cross-linking reaction between pyrocatechol and hexamethylenediamine (HDMA) under oxidizing conditions. For demonstrating the efficacy of this approach, different substrates (glass, gold, silicon, and fabric) have been coated and later functionalized with two different alkylated species (1-hexadecanamine and stearoyl chloride). The success of their attachment has been demonstrated by evaluating the hydrophobicity conferred to the surface by contact angle measurements. Interestingly, these results, together with its chemical characterization by means of X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FT-IR), have proven that the reactivity of the primer coating towards the functionalizing agent can be tuned in function of its generation time.

Replacing Nitrogen by Sulfur: From Structurally Disordered Eumelanins to Regioregular Thiomelanin Polymers

The oxidative polymerization of 5,6-dihydroxybenzothiophene (DHBT), the sulfur analog of the key eumelanin building block 5,6-dihydroxyindole (DHI), was investigated to probe the role of nitrogen in eumelanin build-up and properties. Unlike DHI, which gives a typical black insoluble eumelanin polymer on oxidation, DHBT is converted to a grayish amorphous solid (referred to as thiomelanin) with visible absorption and electron paramagnetic resonance properties different from those of DHI melanin. Mass spectrometry experiments revealed gradational mixtures of oligomers up to the decamer level. Quite unexpectedly, nuclear magnetic resonance (NMR) analysis of the early oligomer fractions indicated linear, 4-, and 7-linked structures in marked contrast with DHI, which gives highly complex mixtures of partially degraded oligomers. Density functional theory (DFT) calculations supported the tendency of DHBT to couple via the 4- and 7-positions. These results uncover the role of nitrogen as a major determinant of the structural diversity generated by the polymerization of DHI, and point to replacement by sulfur as a viable entry to regioregular eumelanin-type materials for potential applications for surface functionalization by dip coating.