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.

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.

Bioinspired catechol-terminated self-assembled monolayers with enhanced adhesion properties.

The role of the catechol moiety in the adhesive properties of mussel proteins and related synthetic materials has been extensively studied in the last years but still remains elusive. Here, a simplified model approach is presented based on a self-assembled monolayer (SAM) of upward-facing catechols thiol-bound to epitaxial gold substrates. The orientation of the catechol moieties is confirmed by spectroscopy, which also showed lack of significant amounts of interfering o-quinones. Local force-distance curves on the SAM measured by atomic force microscopy (AFM) shows an average adhesion force of 45 nN, stronger than that of a reference polydopamine coating, along with higher reproducibility and less statistical dispersion. This is attributed to the superior chemical and topographical homogeneity of the SAM coating. Catechol-terminated SAMs are also obtained on high-roughness gold substrates that show the ability to assemble magnetic nanoparticles, despite their lack of enhanced adhesion at the molecular level. Finally, the influence of the catechol group on the formation and quality of the SAM is explored both theoretically (molecular dynamics simulations) and experimentally using direct-write AFM lithography.

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.

Synthesis, X-ray Structure, and Electrochemical Oxidative Coupling Reactions of 1,5- and 2,6-Bis(1,4-dithiafulven-6-yl)naphthalenes.

Novel pi-extended tetrathiafulvalene (TTF) derivatives (12a-c, 13a-c, 15a-c) in which the two 1,3-dithiole units are connected through a naphthalene spacer have been prepared in high yields by Wittig-Horner olefination reaction from dialkoxy-substituted diformylnaphthalenes (11a,b, 14) and differently substituted phosphonate esters (10a-c). The electrochemical study revealed a similar behavior for the novel electron donor molecules (12a-c, 13a-c, 15a-c) regardless of the position of the 1,3-dithiole rings on the naphthalene core. The extended donors undergo an efficient electrooxidation process affording new oligomeric extended TTF species which exhibit lower oxidation potential values than their precursor donors. EPR experiments confirm the presence of the cation radical derived from the oligomeric TTF vinylogues and support an ECE process. The structural study has been carried out by X-ray analysis of 12a and semiempirical PM3 calculations and reveals a distorted geometry from the planarity with the naphthalene moiety forming an angle of approximately 35 degrees with the thiafulvalene rings. A good agreement was found between the experimental and calculated values, thus validating the PM3 method. The chemical oxidation of the synthesized donors (12a-c, 13a-c, 15a-c) with strong electron acceptors give rise to charge transfer complexes (CTC) which were characterized by UV-vis, FTIR, and EPR spectroscopy.

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.

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.

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.