The deposition of "polydopamine" films, from an aqueous solution containing dopamine or other catecholamines, constitutes a new and versatile way to functionalize solid-liquid interfaces. Indeed such films can be deposited on almost all kinds of materials. Their deposition kinetics does not depend markedly on the surface chemistry of the substrate, and the films can reach thickness of a few tens of nanometers in a single reaction step. Up to now, even if a lot is known about the oxidation mechanism of dopamine in solution, only little information is available to describe the deposition mechanism on surfaces either by oxidation in solution or by electrodeposition. The deposition kinetics of melanin was only investigated from dopamine solutions using oxygen or ammonium persulfate as an oxidant and from a tris(hydroxymethyl) aminomethane (Tris) containing buffer solutions at pH 8.5. Many other oxidants could be used, and the buffer agent containing a primary amine group may influence the deposition process. Herein we show that the deposition kinetics of melanin from dopamine containing buffers at pH 8.5 can be markedly modified using Cu(2+) instead of O2 as an oxidant: the deposition kinetics remains linear up to thicknesses of more than 70 nm, whereas the film growth stops at 45 ± 5 nm in the presence of 02. In addition, the films prepared from Cu(2+) containing solutions display an absorption spectrum with defined peaks at 320 and 370 nm, which are absent in the spectra of films prepared in oxygenated solutions. The replacement of Tris buffer by phosphate buffer also has a marked effect on the melanin deposition kinetics.

Ferroelectrics are multifunctional materials that reversibly change their polarization under an electric field. Recently, the search for new ferroelectrics has focused on organic and bio‐organic materials, where polarization switching is used to record/retrieve information in the form of ferroelectric domains. This progress has opened a new avenue for data storage, molecular recognition, and new self‐assembly routes. Crystalline glycine is the simplest amino acid and is widely used by living organisms to build proteins. Here, it is reported for the first time that γ‐glycine, which has been known to be piezoelectric since 1954, is also a ferroelectric, as evidenced by local electromechanical measurements and by the existence of as‐grown and switchable ferroelectric domains in microcrystals grown from the solution. The experimental results are rationalized by molecular simulations that establish that the polarization vector in γ‐glycine can be switched on the nanoscale level, opening a pathway to novel classes of bioelectronic logic and memory devices.

Diphenylalanine (FF) peptide nanotubes (PNTs) present a unique class of selfassembled functional biomaterials owing to a wide range of useful properties including nanostructural variability, mechanical rigidity, and chemical stability. In addition, a strong piezoelectric activity has been recently observed paving the way to their use as nanoscale sensors and actuators. In this work, we fabricated both horizontal and vertical FF PNTs and examined their optical second harmonic generation and local piezoresponse as a function of temperature. The measurements show gradual decrease of polarization with increasing temperature accompanied by irreversible phase transition into another crystalline phase at about 140-150 ºC. The results are corroborated by the molecular dynamic simulations predicting order-disorder phase transition into centrosymmetric (possibly, orthorhombic) phase with antiparallel polarization orientation in neighboring FF rings. Partial piezoresponse hysteresis indicates incomplete polarization switching due to high coercive field in FF PNTs.

Polydopamine films have been introduced by Messersmith et al. as a possible "versatile" surface functionalization method allowing to coat the surface of almost all known materials even superhydrophobic surfaces. These new kinds of coatings also confer a plethora of functionalities to the coated materials owing to the complex chemistry of the catechol quinone moieties present on the surface of polydopamine. These coatings may hence become an interesting alternative to established surface coatings like selfassembled monolayers and polyelectrolyte multilayered films. In this review, we describe the knowledge acquired in the last 3 years about the deposition mechanisms of polydopamine films, their properties, and various applications in surface science at the nanoscale.

Eumelanin is not only a ubiquitous pigment among living organisms with photoprotective and antioxidant functions, but is also the subject of intense interest in materials science due to its photoconductivity and as a possible universal coating platform, known as "polydopamine films". The structure of eumelanin remains largely elusive, relying either on a polymeric model or on a heterogeneous aggregate structure. The structure of eumelanin as well as that of the closely related "polydopamine films" can be modified by playing on the nature of the oxidant used to oxidize dopamine or related compounds. In this investigation, we show that dopamine-eumelanins produced from dopamine in the presence of either air (O2 being the oxidant) or Cu(2+) cations display drastically different optical and colloidal properties in relation with a different supramolecular assembly of the oligomers of 5,6 dihydroxyindole, the final oxidation product of dopamine. The possible origin of these differences is discussed on the basis of Cu(2+) incorporation in Cu dopamine-eumelanin.