Biosustainable Hybrid Nanoplatforms as Photoacoustic Agents.

The development of biosafe theranostic nanoplatforms has attracted great attention due to their multifunctional behavior, reduced potential toxicity, and improved long-term safety. When considering photoacoustic contrast agents and photothermal conversion tools, melanin and constructs like melanin are highly appealing due to their ability to absorb optical energy and convert it into heat. Following a sustainable approach, in this study, silver-melanin like-silica nanoplatforms are synthesized exploiting different bio-available and inexpensive phenolic acids as potential melanogenic precursors and exploring their role in tuning the final systems architecture. The UV-Vis combined with X-Ray Diffraction investigation proves metallic silver formation, while Transmission Electron Microscopy analysis reveals that different morphologies can be obtained by properly selecting the phenolic precursors. By looking at the characterization results, a tentative formation mechanism is proposed to explain how phenolic precursors' redox behavior may affect the nanoplatforms' structure. The antibacterial activity experiments showed that all synthesized systems have a strong inhibitory effect on Escherichia coli, even at low concentrations. Furthermore, very sensitive Photoacoustic Imaging capabilities and significant photothermal behavior under laser irradiation are exhibited. Finally, a marked influence of phenol nature on the final system architecture is revealed resulting in a significant effect on both biological and photoacoustic features of the obtained systems. These melanin-based hybrid systems exhibit excellent potential as triggerable nanoplatforms for various biomedical applications.

Cyan Hydrogen Process: A New Route for Simultaneous Hydrogen Production and Carbon Valorization.

Hydrogen is expected to largely contribute to the near-future circular economy. Today, most hydrogen is still produced from fossil fuels or renewable pathways with low efficiency and high cost. Herein, a proof of concept for a novel hydrogen production process is proposed, here named cyan hydrogen, inspired by a combination of the green and blue processes, due to the key role played by water and the low carbon content in the gas phase, respectively. The developed novel process, recently patented and demonstrated at the lab scale, is based on successive steps in which ethanol (5.0 mL) and water (10.0 mL) are alternately fed, with a fixed initial amount of sodium metaborate (2.0 g), in a batch reactor at 300 °C. Preliminary results showed the simultaneous production of a 95% v/v hydrogen stream, a polymeric byproduct with a repetitive carbon pattern -CH2-CH2-, and a liquid phase rich in oxygenated chemicals at temperatures lower than conventional hydrogen production processes.

Designing bioinspired multifunctional nanoplatforms to support wound healing and skin regeneration: Mg-hydroxyapatite meets melanins.

Melanin is a multifunctional biological pigment that recently emerged as endowed with anti-inflammatory, antioxidant, and antimicrobial properties and with high potentialities in skin protection and regenerative medicine. Here, a biomimetic magnesium-doped nano-hydroxyapatite (MgHA) was synthesized and decorated with melanin molecules starting from two different monomeric precursors, i.e. 5,6-dihydroxyindole-2-carboxylic acid (DHICA) and dopamine (DA), demonstrating to be able to polymerize on the surface of MgHA nanostructures, thus leading to a melanin coating. This functionalization was realized by a simple and green preparation method requiring mild conditions in an aqueous medium and room temperature. Complementary spectroscopy and electron imaging analyses were carried out to define the effective formation of a stable coating, the percentage of the organic compounds, and the structural properties of resulting melanin-coated nanostructures, which showed good antioxidant activity. The in vitro interaction with a cell model, i.e. mouse fibroblasts, was investigated. The excellent biocompatibility of all bioinspired nanostructures was confirmed from a suitable cell proliferation. Finally, the enhanced biological performances of the nanostructures coated with melanin from DHICA were confirmed by scratch assays. Jointly our findings indicated that low crystalline MgHA and melanin pigments can be efficiently combined, and the resulting nanostructures are promising candidates as multifunctional platforms for a more efficient approach for skin regeneration and protection.

Enhanced Photoacoustic Response by Synergistic Ag-Melanin Interplay at the Core of Ternary Biocompatible Hybrid Silica-Based Nanoparticles.

Photoacoustics (PA) is gaining increasing credit among biomolecular imaging methodologies by virtue of its poor invasiveness, deep penetration, high spatial resolution, and excellent endogenous contrast, without the use of any ionizing radiation. Recently, we disclosed the excellent PA response of a self-structured biocompatible nanoprobe, consisting of ternary hybrid nanoparticles with a silver core and a melanin component embedded into a silica matrix. Although preliminary evidence suggested a crucial role of the Ag sonophore and the melanin-containing nanoenvironment, whether and in what manner the PA response is controlled and affected by the self-structured hybrid nanosystems remained unclear. Because of their potential as multifunctional platforms for biomedical applications, a detailed investigation of the metal-polymer-matrix interplay underlying the PA response was undertaken to understand the physical and chemical factors determining the enhanced response and to optimize the architecture, composition, and performance of the nanoparticles for efficient imaging applications. Herein, we provide the evidence for a strong synergistic interaction between eumelanin and Ag which suggests an important role in the in situ-generated metal-organic interface. In particular, we show that a strict ratio between melanin and silver precursors and an accurate choice of metal nanoparticle dimension and the kind of metal are essential for achieving strong enhancements of the PA response. Systematic variation of the metal/melanin component is thus shown to offer the means of tuning the stability and intensity of the photoacoustic response for various biomedical and theranostic applications.

Towards nanostructured red-ox active bio-interfaces: Bioinspired antibacterial hybrid melanin-CeO2 nanoparticles for radical homeostasis.

Redox-active nano-biointerfaces are gaining weight in the field of regenerative medicine since they can act as enzymes in regulating physiological processes and enabling cell homeostasis, as well as the defense against pathogen aggression. In particular, cerium oxide nanoparticles (CeO2 NPs) stand as intriguing enzyme-mimicking nanoplatforms, owing to the reversible Ce+3/Ce+4 surface oxidation state. Moreover, surface functionalization leads to higher catalytic activity and selectivity, as well as more tunable enzyme-mimicking performances. Conjugation with melanin is an adequate strategy to boost and enrich CeO2 NPs biological features, because of melanin redox properties accounting for intrinsic antioxidant, antimicrobial and anti-inflammatory power. Herein, hybrid Melanin/CeO2 nanostructures were designed by simply coating the metal-oxide nanoparticles with melanin chains, obtained in-situ through ligand-to-metal charge transfer mechanism, according to a bioinspired approach. Obtained hybrid nanostructures underwent detailed physico-chemical characterization. Morphological and textural features were investigated through TEM, XRD and N2 physisorption. The nature of nanoparticle-melanin interaction was analyzed through FTIR, UV-vis and EPR spectroscopy. Melanin-coated hybrid nanostructures exhibited a relevant antioxidant activity, confirmed by a powerful quenching effect for DPPH radical, reaching 81 % inhibition at 33 µg/mL. A promising anti-inflammatory efficacy of the melanin-coated hybrid nanostructures was validated through a significant inhibition of BSA denaturation after 3 h. Meanwhile, the enzyme-mimicking activity was corroborated by a prolonged peroxidase activity after 8 h at 100 µg/mL and a relevant catalase-like action, by halving the H2O2 level in 30 min at 50 µg/mL. Antimicrobial assays attested that conjugation with melanin dramatically boosted CeO2 biocide activity against both Gram (-) and Gram (+) strains. Cytocompatibility tests demonstrated that the melanin coating not only enhanced the CeO2 nanostructures biomimicry, resulting in improved cell viability for human dermal fibroblast cells (HDFs), but mostly they proved that Melanin-CeO2 NPs were able to control the oxidative stress, modulating the production of nitrite and reactive oxygen species (ROS) levels in HDFs, under physiological conditions. Such remarkable outcomes make hybrid melanin-CeO2 nanozymes, promising redox-active interfaces for regenerative medicine.

Nanoparticle Coatings on Glass Surfaces to Prevent Pseudomonas fluorescens AR 11 Biofilm Formation.

Microbial colonization of surfaces is a sanitary and industrial issue for many applications, leading to product contamination and human infections. When microorganisms closely interact with a surface, they start to produce an exo-polysaccaridic matrix to adhere to and protect themselves from adverse environmental conditions. This type of structure is called a biofilm. The aim of our work is to investigate novel technologies able to prevent biofilm formation by surface coatings. We coated glass surfaces with melanin-ZnO2, melanin-TiO2, and TiO2 hybrid nanoparticles. The functionalization was performed using cold plasma to activate glass-substrate-coated surfaces, that were characterized by performing water and soybean oil wetting tests. A quantitative characterization of the antibiofilm properties was done using Pseudomonas fluorescens AR 11 as a model organism. Biofilm morphologies were observed using confocal laser scanning microscopy and image analysis techniques were used to obtain quantitative morphological parameters. The results highlight the efficacy of the proposed surface coating to prevent biofilm formation. Melanin-TiO2 proved to be the most efficient among the particles investigated. Our results can be a valuable support for future implementation of the technique proposed here in an extended range of applications that may include further testing on other strains and other support materials.

Bioactive Composite Methacrylated Gellan Gum for 3D-Printed Bone Tissue-Engineered Scaffolds.

Gellan gum (GG) was chemically modified with methacrylic moieties to produce a photocrosslinkable biomaterial ink, hereinafter called methacrylated GG (GGMA), with improved physico-chemical properties, mechanical behavior and stability under physiological conditions. Afterwards, GGMA was functionalized by incorporating two different bioactive compounds, a naturally derived eumelanin extracted from the black soldier fly (BSF-Eumel), or hydroxyapatite nanoparticles (HAp), synthesized by the sol-gel method. Different ink formulations based on GGMA (2 and 4% (w/v)), BSF-Eumel, at a selected concentration (0.3125 mg/mL), or HAp (10 and 30% wHAp/wGGMA) were developed and processed by three-dimensional (3D) printing. All the functionalized GGMA-based ink formulations allowed obtaining 3D-printed GGMA-based scaffolds with a well-organized structure. For both bioactive signals, the scaffolds with the highest GGMA concentration (4% (w/v)) and the highest percentage of infill (45%) showed the best performances in terms of morphological and mechanical properties. Indeed, these scaffolds showed a good structural integrity over 28 days. Given the presence of negatively charged groups along the eumelanin backbone, scaffolds consisting of GGMA/BSF-Eumel demonstrated a higher stability. From a mechanical point of view, GGMA/BSF-Eumel scaffolds exhibited values of storage modulus similar to those of GGMA ones, while the inclusion of HAp at 30% (wHAp/wGGMA) led to a storage modulus of 32.5 kPa, 3.5-fold greater than neat GGMA. In vitro studies proved the capability of the bioactivated 3D-printed scaffolds to support 7F2 osteoblast cell growth and differentiation. BSF-Eumel and HAp triggered a different time-dependent physiological response in the osteoblasts. Specifically, while the ink with BSF-Eumel acted as a stimulus towards cell proliferation, reaching the highest value at 14 days, a higher expression of alkaline phosphatase activity was detected for scaffolds consisting of GGMA and HAp. The overall findings demonstrated the possible use of these biomaterial inks for 3D-printed bone tissue-engineered scaffolds.

Eumelanin decorated poly(lactic acid) electrospun substrates as a new strategy for spinal cord injury treatment.

Spinal cord injury (SCI) is characterized by neuroinflammatory processes that are marked by an uncontrolled activation of microglia, which directly damages neurons. Natural and synthetic melanins represent an effective tool to treat neuroinflammation because they possess immunomodulatory properties. Here, the main objective was to evaluate the effect of eumelanin-coated poly(lactic acid) (EU@PLA) aligned microfibers on in vitro model of neuroinflammation related to spinal cord injury in terms of inflammatory mediators' modulation. Aligned fibers were chosen to provide physical cues to guide axonal growth in a specific direction thus restoring the synaptic connection. Eumelanin decorated PLA electrospun substrates were produced combining electrospinning, spin coating and solid-state polymerization processes (oxidative coupling under oxygen atmosphere). Biological response in terms of antioxidant and anti-inflammatory activity was analyzed on an in vitro model of neuroinflammation [microglial cells stimulated with lipopolysaccharide (LPS)]. Cell morphology and EU@PLA mechanism of action, in terms of toll-like receptor-4 (TLR-4) involvement were assessed. The results show that EU@PLA fibers were able to decrease reactive oxygen species, nuclear factor kappa-light-chain-enhancer of activated B cells (NF-кB) expression >50 % compared to PLA + LPS and interleukin 6 (IL-6) secretion about 20 %. Finally, the mechanism of action of EU@PLA in microglia was found to be dependent on the TLR-4 signaling. Protein expression analysis revealed a decreased in TLR-4 production induced by LPS stimulation in presence of EU@PLA. Overall, our results show that EU@PLA represents an innovative and effective strategy for the control of inflammatory response in central nervous system.

High density polyethylene (HDPE) biodegradation by the fungus Cladosporium halotolerans.

Polyethylene (PE) is high molecular weight synthetic polymer, very hydrofobic and hardly biodegradable. To increase polyethylene bio-degradability it is very important to find microorganisms that improve the PE hydrophilic level and/or reduce the length of its polymeric chain by oxidation. In this study, we isolated Cladosporium halotolerans, a fungal species, from the gastric system of Galleria mellonella larvae. Here, we show that C. halotolerans grows in the presence of PE polymer, it is able to interact with plastic material through its hyphae and secretes enzymes involved in PE degradation.

Eumelanin from the Black Soldier Fly as Sustainable Biomaterial: Characterisation and Functional Benefits in Tissue-Engineered Composite Scaffolds.

An optimized extraction protocol for eumelanins from black soldier flies (BSF-Eumel) allows an in-depth study of natural eumelanin pigments, which are a valuable tool for the design and fabrication of sustainable scaffolds. Here, water-soluble BSF-Eumel sub-micrometer colloidal particles were used as bioactive signals for developing a composite biomaterial ink for scaffold preparation. For this purpose, BSF-Eumel was characterized both chemically and morphologically; moreover, biological studies were carried out to investigate the dose-dependent cell viability and its influence on human mesenchymal stem cells (hMSCs), with the aim of validating suitable protocols and to find an optimal working concentration for eumelanin-based scaffold preparation. As proof of concept, 3D printed scaffolds based on methacrylated hyaluronic acid (MEHA) and BSF-Eumel were successfully produced. The scaffolds with and without BSF-Eumel were characterized in terms of their physico-chemical, mechanical and biological behaviours. The results showed that MEHA/BSF-Eumel scaffolds had similar storage modulus values to MEHA scaffolds. In terms of swelling ratio and stability, these scaffolds were able to retain their structure without significant changes over 21 days. Biological investigations demonstrated the ability of the bioactivated scaffolds to support the adhesion, proliferation and osteogenic differentiation of human mesenchymal stem cells.

Eumelanin pigment precursor 2-carboxy-5,6-dihydroxyindole and 2-amino-6-methylbenzothiazole chromophore integration towards melanin inspired chemoresponsive materials: the case of the Zn2+ ion.

The 2-amino-6-methylbenzothiazole chromophore is introduced at the carboxyl group of the melanin precursor 2-carboxy-5,6-dihydroxyindole achieving a novel dihydroxyindole derivative with metal chelation properties not depending on the catechol moiety. In view of potential exploitation in charge storage systems, systematic investigation of the interaction of the new amide derivative with metal ions is carried out, in comparison with that of the parent 2-carboxy-5,6-dihydroxyindole, and the stoichiometry of the zinc-amide complex is determined.

The interplay of chemical structure, physical properties, and structural design as a tool to modulate the properties of melanins within mesopores.

The design of modern devices that can fulfil the requirements for sustainability and renewable energy applications calls for both new materials and a better understanding of the mixing of existing materials. Among those, surely organic-inorganic hybrids are gaining increasing attention due to the wide possibility to tailor their properties by accurate structural design and materials choice. In this work, we'll describe the tight interplay between porous Si and two melanic polymers permeating the pores. Melanins are a class of biopolymers, known to cause pigmentation in many living species, that shows very interesting potential applications in a wide variety of fields. Given the complexity of the polymerization process beyond the formation and structure, the full understanding of the melanins' properties remains a challenging task. In this study, the use of a melanin/porous Si hybrid as a tool to characterize the polymer's properties within mesopores gives new insights into the conduction mechanisms of melanins. We demonstrate the dramatic effect induced on these mechanisms in a confined environment by the presence of a thick interface. In previous studies, we already showed that the interactions at the interface between porous Si and eumelanin play a key role in determining the final properties of composite materials. Here, thanks to a careful monitoring of the photoconductivity properties of porous Si filled with melanins obtained by ammonia-induced solid-state polymerization (AISSP) of 5,6-dihydroxyindole (DHI) or 1,8-dihydroxynaphthalene (DHN), we investigate the effect of wet, dry, and vacuum cycles of storage from the freshly prepared samples to months-old samples. A computational study on the mobility of water molecules within a melanin polymer is also presented to complete the understanding of the experimental data. Our results demonstrate that: (a) the hydration-dependent behavior of melanins is recovered in large pores (≈ 60 nm diameter) while is almost absent in thinner pores (≈ 20 nm diameter); (b) DHN-melanin materials can generate higher photocurrents and proved to be stable for several weeks and more sensitive to the wet/dry variations.

Promelanogenic Effects by an Annurca Apple-Based Natural Formulation in Human Primary Melanocytes.

INTRODUCTION: Melanocytes are engaged in synthesis, transport, and release of pigments at the epidermal-melanin units in response to the finely regulated melanogenic pathway. A multifaceted combination of both intrinsic and extrinsic factors - from endocrine and paracrine dynamics to exogenous stimuli such as sunlight and xenobiotics - modulates expression and activity of proteins involved in pigmentation, including the rate-limiting enzyme tyrosinase. As well as playing critical physiological functions comprising skin photoprotection, melanins define hair and skin pigmentation which in turn have impacted considerably to human social communication since time immemorial. Additionally, numerous skin diseases based on pigmentation alterations can have serious public influence. While several melanogenesis inhibitors are already available, the number of melanin activators and tyrosinase stimulators as drug-like agents is still limited. METHODS: To explore the biological effects of an Annurca Apple-based nutraceutical preparation (AMS) on melanin production, experiments in cellular models of human skin were performed. Both primary cultures and co-cultures of epidermal melanocytes (HEMa) and follicular keratinocytes (HHFK) were used. RESULTS: We show that AMS, by now branded for its cutaneous beneficial effects, induces in total biocompatibility a significant promelanogenic effect in human primary melanocytes. In line, we found melanin cytosolic accumulation consistent with tyrosinase up-regulation. CONCLUSION: Disposal of skin pigmenting agents would be attractive for the treatment of hypopigmentation disorders, to postpone skin photoaging or simply for fashion, so that discovery and development of melanogenesis stimulators, especially from natural sources, is nowadays a dynamic area of research.

Bioinspired antibacterial PVA/Melanin-TiO2 hybrid nanoparticles: the role of poly-vinyl-alcohol on their self-assembly and biocide activity.

Hybrid Melanin-TiO2 nanoparticles are promising bioinspired antibacterial agents for biomedical coatings and food-packaging fields. However, due to a very low colloidal stability, they showed a high tendency to self-aggregate and rapidly precipitate, making not easy their use in aqueous medium to produce homogeneous antimicrobial coatings or nanocomposites. A valid strategy to improve their dispersion is the combination with a hydrophilic water-soluble polymer such as poly-vinyl-alcohol (PVA), which is a good choice to improve the colloidal stability of nanoparticles and to modulate their agglomeration. In this work, we propose an in-situ synthetic approach based on the hydrothermal route, by which the hybrid Melanin-TiO2 nanoparticles were prepared starting from the inorganic and organic precursors in the presence of PVA. Combined approach of TEM, XRD, TG/DSC, EPR and DLS techniques allows for assessing the PVA role in the formation of hybrids and on their morphological features as well as colloidal stability and aqueous dispersion. Antibacterial tests demonstrated the biocide activity of PVA/Melanin-TiO2 nanoparticles against Escherichia coli bacterial cultures, which resulted partially influenced by the PVA content. This study provides key information on the mutual influence of organic/inorganic components on the functional properties of the final hybrid nanocomposites, contributing to define a much more far-reaching implementation in the synthesis of bioinspired polymer-based nanocomposites.

Melanin and Melanin-Like Hybrid Materials in Regenerative Medicine.

Melanins are a group of dark insoluble pigments found widespread in nature. In mammals, the brown-black eumelanins and the reddish-yellow pheomelanins are the main determinants of skin, hair, and eye pigmentation and play a significant role in photoprotection as well as in many biological functions ensuring homeostasis. Due to their broad-spectrum light absorption, radical scavenging, electric conductivity, and paramagnetic behavior, eumelanins are widely studied in the biomedical field. The continuing advancements in the development of biomimetic design strategies offer novel opportunities toward specifically engineered multifunctional biomaterials for regenerative medicine. Melanin and melanin-like coatings have been shown to increase cell attachment and proliferation on different substrates and to promote and ameliorate skin, bone, and nerve defect healing in several in vivo models. Herein, the state of the art and future perspectives of melanins as promising bioinspired platforms for natural regeneration processes are highlighted and discussed.

Albumin-Modified Melanin-Silica Hybrid Nanoparticles Target Breast Cancer Cells via a SPARC-Dependent Mechanism.

Bioconjugation of a recently developed photoacoustic nanoprobe, based on silica-templated eumelanin-silver hybrid nanoparticles (MelaSil_Ag-NPs), with human serum albumin (HSA) is disclosed herein as an efficient and practical strategy to improve photostability and to perform SPARC mediated internalization in breast cancer cells. Modification of NPs with HSA induced a slight viability decrease in breast cancer cells (HS578T) and normal breast cells (MCF10a) when incubated with HSA-NPs up to 100 µg/mL concentration for 72 h and a complete suppression of hemotoxicity for long incubation times. Uptake experiments with MelaSil_Ag-HSA NPs indicated very high and selective internalization via SPARC in HS578T (SPARC positive cells) but not in MCF10a (SPARC negative cells), as evaluated by using endocytosis inhibitors. The binding of SPARC to HSA was confirmed by Co-IP and Dot-blot assays. Additional studies were performed to analyze the interaction of MelaSil_Ag-HSA NPs with protein corona. Data showed a dramatic diminution of interacting proteins in HSA conjugated NPs compared to bare NPs. HSA-coated MelaSil_Ag-NPs are thus disclosed as a novel functional nanohybrid for potential photoacoustic imaging applications.

Eumelanin Precursor 2-Carboxy-5,6-Dihydroxyindole (DHICA) as Doping Factor in Ternary (PEDOT:PSS/Eumelanin) Thin Films for Conductivity Enhancement.

The integration of the pristine not-doped commercial poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) PH1000 with eumelanin, the brown to black kind of melanin pigment, was achieved by dissolving the melanogenic precursors 2-carboxy-5,6-dihydroxyindole (DHICA) in the PH1000 suspension. Solid state oxidative polymerization of the catecholic indole allowed obtaining the ternary blend PEDOT:PSS/eumelanin. The introduction of DHICA into PH1000 produced a noticeable increase in the conductivity of PEDOT thin films akin to that produced by dimethyl sulfoxide (DMSO) treatment, opening up novel strategies for the simultaneous integration of eumelanin polymer and conductivity enhancement of PEDOT containing coatings, as well as the long term goal of replacing PSS by DHICA eumelanin for PEDOT pairing.

Relation between Local Structure, Electric Dipole, and Charge Carrier Dynamics in DHICA Melanin: A Model for Biocompatible Semiconductors.

Eumelanins are a family of natural and synthetic pigments obtained by oxidative polymerization of their natural precursors: 5,6-dihydroxyindole and its 2-carboxy derivative (DHICA). The simultaneous presence of ionic and electronic charge carriers makes these pigments promising materials for applications in bioelectronics. In this computational study we build a structural model of DHICA melanin considering the interplay between its many degrees of freedom, and then we examine the electronic structure of representative oligomers. We find that a nonvanishing dipole along the polymer chain sets this system apart from conventional polymer semiconductors, determining its electronic structure, reactivity toward oxidation and localization of the charge carriers. Our work sheds light on previously unnoticed features of DHICA melanin that not only fit well with its radical scavenging and photoprotective properties but also open new perspectives toward understanding and tuning charge transport in this class of materials.

En Route to a Chiral Melanin: The Dynamic "From-Imprinted-to-Template" Supramolecular Role of Porphyrin Hetero-Aggregates During the Oxidative Polymerization of L-DOPA.

Chiral porphyrin hetero-aggregates, produced from meso-tetrakis(4-N-methylpyridyl) porphyrin H2T4 and copper(II) meso-tetrakis(4-sulfonatophenyl)porphyrin CuTPPS by an imprinting effect in the presence of L-3,4-dihydroxyphenylalanine (L-DOPA), are shown herein to serve as templates for the generation of chiral structures during the oxidative conversion of the amino acid to melanin. This remarkable phenomenon is suggested to involve the initial role of L-DOPA and related chiral intermediates like dopachrome as templates for the production of chiral porphyrin aggregates. When the entire chiral pool from DOPA is lost, chiral porphyrin hetero-aggregate would elicit axially chiral oligomer formation from 5,6-dihydroxyindole intermediates in the later stages of melanin synthesis. These results, if corroborated by further studies, may open unprecedented perspectives for efficient strategies of asymmetric melanin synthesis with potential biological and technological applications.

On the antioxidant activity of eumelanin biopigments: a quantitative comparison between free radical scavenging and redox properties.

The antioxidant activity of eumelanin, a ubiquitous pigment in flora and fauna, constitutes one of its most fascinating physicochemical properties. To shed light on free radical scavenging vs redox facets of such activity, we applied hydrogen atom transfer- and electron transfer-based assays to pristine Sepia ink, eumelanin from Sepia ink, chemically controlled eumelanins and their precursor building blocks. Our work contributes to the rational use of the antioxidant properties of eumelanin for health, cosmetics and environmental applications.