The Biopigment Eumelanin in the Sustainability Challenge: Interfaces With Metal Electrodes, UV-Absorption Enhancement of Plastics and its Biodegradability

L’Organisation des Nations Unies (ONU) définit le développement durable comme la capacité d’une génération de satisfaire ses propres besoins « sans compromettre la possibilité des générations suivantes de satisfaire les leurs ». Le domaine de l’électronique est marqué par la croissance effrénée des déchets d’équipements électriques et électroniques (DEEE) et par l’épuisement des ressources nécessaires à la fabrication des EEE. L’utilisation de matériaux organiques (constitués de carbone) naturels (biosourcés), biodégradables et traités à l’aide de solvants non toxiques, est alors une solution à considérer pour réduire l’empreinte écologique de l’électronique. L’eumélanine, sous-catégorie noire/marron de la mélanine (pigment omniprésent dans la faune et la flore), présente une absorption optique étendue sur les spectres ultraviolet (UV) et visible, une réponse électrique dépendante du niveau d’hydratation, des propriétés de chélation des métaux et de piégeage des radicaux ainsi qu’une structure moléculaire qui comporte des groupements fonctionnels redox. L’eumélanine est donc un matériau prometteur dans l’électronique organique verte. L’électronique organique utilise des matériaux conducteurs ou semiconducteurs à base de carbone, qui présentent une alternance de liaisons simples et doubles carbone-carbone (systèmes conjugués). Ces matériaux, outre leur flexibilité mécanique, peuvent être traités en solution. Les dispositifs à base de matériaux organiques se distinguent, par conséquent, par leur faible énergie intrinsèque (l’énergie consommée pendant leur fabrication), comparés à la majorité des dispositifs à base de matériaux inorganiques pour lesquels le processus de fabrication implique de hautes températures et des très baisses pressions (vide élevé). Les efforts pour rendre le développement plus durable concernent aussi les matériaux organiques isolants (plastiques) pour les emballages et leurs additifs nécessaires pour améliorer certaines propriétés telles que la stabilité thermique et l’absorption des rayons UV. Le coeur de cette thèse est consacré à l’étude de plusieurs propriétés fonctionnelles de l’eumélanine dans le cadre d’une utilisation potentielle dans les technologies liées à l’électronique organique verte ainsi que dans le domaine des additifs plus respectueux de l’environnent pour les plastiques. Le Chapitre 1 présente la mélanine, avec une attention particulière portée à l’eumélanine et ses propriétés.----------Abstract The United Nations define sustainability as the ability to meet one generation’s needs “without compromising the ability of future generations to meet their own needs”. The field of electronics features a dramatic increase of waste electrical and electronic equipment (WEEE) and the depletion of key elements necessary for EEE fabrication. The use of biodegradable organic (carbon-based) materials extracted from natural sources (bio-sourced) and processed with non-toxic solvents represents a valuable option to alleviate the environmental footprint of the electronic sector. Eumelanin, a dark-brown subcategory of melanins (a ubiquitous biopigment in flora and fauna), features broad ultraviolet-visible absorption, hydration-dependent electrical response as well as metal chelation, radical scavenging and redox activity. Eumelanin is a promising candidate in the field of green (sustainable) organic electronics. Organic (plastic) electronics is based on carbon-based conducting and semiconducting polymers and small molecules that feature conjugation (alternance of single and double carbon-carbon bonds) in their molecular structure. In addition of being mechanically flexible, devices based on organic electronic materials can be solution-processable and thus stand for their lower embodied energy (i.e. “energy spent in the production phase and stored in the inner constituents”) with respect to most inorganic ones, which are processed at high-temperature and under high-vacuum conditions. Sustainability is an issue also in the field of (non-conducting) plastics for packaging, where it concerns not only the packaging polymers but also the additives needed to enhance certain properties, such as thermal stability or ultraviolet (UV) radiation absorption. The core of this PhD thesis is devoted to the study of a number of functional properties of eumelanin in view of its use in sustainable organic electronic technologies as well as a greener additive for plastic packaging. Chapter 1 gives an overview on melanins, with a focus on the subcategory eumelanin and its properties. Chapter 2 provides a review of the state of the art of the potential applications of eumelanin demonstrated in the literature. Chapter 3 details the targets of the research: the investigation of eumelanin-metal interfaces under bias, the study of eumelanin as an additive for plastics and the assessment of eumelanin’s biodegradability. Chapter 4 briefly explains the characterization techniques used

Biodegradation of bio-sourced and synthetic organic electronic materials towards green organic electronics

Ubiquitous use of electronic devices has led to an unprecedented increase in related waste as well as the worldwide depletion of reserves of key chemical elements required in their manufacturing. The use of biodegradable and abundant organic (carbon-based) electronic materials can contribute to alleviate the environmental impact of the electronic industry. The pigment eumelanin is a bio-sourced candidate for environmentally benign (green) organic electronics. The biodegradation of eumelanin extracted from cuttlefish ink is studied both at 25 °C (mesophilic conditions) and 58 °C (thermophilic conditions) following ASTM D5338 and comparatively evaluated with the biodegradation of two synthetic organic electronic materials, namely copper (II) phthalocyanine (Cu–Pc) and polyphenylene sulfide (PPS). Eumelanin biodegradation reaches 4.1% (25 °C) in 97 days and 37% (58 °C) in 98 days, and residual material is found to be without phytotoxic effects. The two synthetic materials, Cu–Pc and PPS, do not biodegrade; Cu–Pc brings about the inhibition of microbial respiration in the compost. PPS appears to be potentially phytotoxic. Finally, some considerations regarding the biodegradation test as well as the disambiguation of “biodegradability” and “bioresorbability” are highlighted

An electrochemical study of natural and chemically controlled eumelanin

Eumelanin is the most common form of the pigment melanin in the human body, with functions including antioxidant behavior, metal chelation, and free radical scavenging. This biopigment is of interest for biologically derived batteries and supercapacitors. In this work, we characterized the voltammetric properties of chemically controlled eumelanins produced from 5,6-dihydroxyindole (DHI) and 5,6-dihydroxyindole-2-carboxylic acid (DHICA) building blocks, namely, DHI-melanin, DHICA-melanin, and natural eumelanin, extracted from the ink sac of cuttlefish, Sepia melanin. Eumelanin electrodes were studied for their cyclic voltammetric properties in acidic buffers including Na+, K+, NH4+, and Cu2+ ions

Characterizing the building blocks of Problematic Use of the Internet (PUI): The role of obsessional impulses and impulsivity traits among Italian young adults

BACKGROUND: Problematic Use of the Internet (PUI) is a considerable issue of the modern era, but its risk factors are still poorly understood. Impulsivity and obsessive-compulsive symptoms have been associated with PUI, but this relationship is still debated. In this article we focus on the relationships of PUI with obsessive-compulsive and impulsive symptoms in a cohort of Italian young adults, in order to identify possible vulnerability factors for PUI.METHODS: A sample of 772 Italian individuals aged 18-30 (mean age 23.3±3.3years old; 38% males and 62% females) was assessed via online survey using the Internet Addiction Test (IAT), the Mini International Neuropsychiatric Interview (MINI) Screen, the Padua Inventory-Washington State University Revision (PI-WSUR) and the Barratt Impulsiveness Scale (BIS-11).RESULTS: Ninety-seven subjects (12.6% of the sample) reported IAT scores at risk for PUI. PUI participants reported higher levels of impulsivity, obsessive-compulsive symptoms and a higher burden of co-occurrent psychiatric symptoms. In a logistic regression model, obsessional impulses to harm (OR =1.108, p<0.001), attentional impulsivity (OR=1.155, p<0.001) and depressive symptomatology (OR=1.246, p=0.012) had significant association with PUI. Finally, higher severity of PUI has been associated with manic/psychotic symptoms and with attentional impulsivity.CONCLUSIONS: Our findings confirmed the role of impulsivity in PUI, while also underling the association of obsessional impulses with this pathological behavior. We could hypothesize a trigger role of obsessive impulses for the engagement in PUI, together with factors as negative affective states. Further research is needed with respect to more severe forms of PUI, also for establishing tailored interventions

Influence of Spray-Drying and Room Temperature Storage on the Anti- and Prooxidant Properties of Fermented Juçara Pulp

Mnoge vrste voća i povrća sadržavaju spojeve koji imaju antioksidacijska svojstva, no njihova prerada i skladištenje u prehrambenim pogonima mogu oštetiti te vrijedne sastojke i dovesti do nastanka slobodnih radikala koji zatim uzrokuju oksidacijski stres. Svrha je ovoga rada bila ispitati in vitro antioksidacijski i prooksidacijski učinak pulpe plodova palme Euterpe edulis (juçara) fermentirane s pomoću bakterija Lactobacillus reuteri ili Lactobacillus plantarum, i to prije i nakon sušenja raspršivanjem uz uporabu maltodekstrina, arapske gume ili želatine kao nosača te skladištenja pri 25 °C tijekom 90 dana. Antioksidacijski učinak je procijenjen na osnovi sposobnosti uklanjanja reaktivnih kisikovih spojeva (ROS) tijekom oksidativnog praska neutrofila i slobodnih 2,2-difenil-1-pikril hidrazil (DPPH) radikala, te određivanjem ukupnog udjela fenolnih spojeva. Prooksidacijski učinak je ispitan mjerenjem količine oslobođenih radikala pomoću elektronske paramagnetske rezonancije (EPR). Fermentacija s pomoću obje bakterije povećala je antioksidacijsku aktivnost, dok je sušenje raspršivanjem smanjilo udjel fenolnih spojeva za 65-85 % te sposobnost uklanjanja DPPH radikala, ovisno o upotrijebljenom nosaču. Svi su uzorci inhibirali ROS tijekom oksidativnog praska neutrofila, pri čemu je pulpa fermentirana s pomoću L. reuteri i sušena uz dodatak arapske gume kao nosača imala najveći učinak. Sušenje raspršivanjem nije utjecalo na intenzitet ili vrstu slobodnih radikala detektiranih pomoću metode EPR. Međutim, skladištenjem na sobnoj temperaturi smanjio se antioksidacijski učinak i povećala količina oslobođenih radikala iz fermentirane pulpe.Many fruits and vegetables contain compounds with antioxidant properties, but the processing and storage conditions of the food industry may damage these beneficial compounds and produce free radicals that are associated with oxidative stress. This study aims to evaluate in vitro the antioxidant capacity and prooxidant effects of juçara pulp fermented with Lactobacillus reuteri or Lactobacillus plantarum before and after spray-drying with maltodextrin, gum arabic or gelatin and storage at 25 °C for 90 days. The antioxidant capacity was assessed by measuring the ability to scavenge reactive oxygen species (ROS) in the neutrophil respiratory burst and free radical 2,2-diphenyl-1-picryl-hydrazyl (DPPH), and by determining the total phenolic content. The prooxidant effects were analyzed as free radical formation measured by electronic paramagnetic resonance (EPR). Fermentation by both bacteria increased the antioxidant activity, while the spray-drying process decreased the content of phenolic compounds (65-85 %) and the DPPH scavenging ability, depending on the carrier usage. All of the samples inhibited ROS in the neutrophil burst, and the juçara pulp fermented by L. reuteri and dried with gum arabic exhibited the best performance. Spray-drying did not influence the intensity or type of free radicals detected by EPR. However, storage at room temperature decreased the antioxidant capacity and increased free radical formation

An electrochemical study of natural and chemically controlled eumelanin

ABSTRACT: Eumelanin is the most common form of the pigment melanin in the human body, with functions including antioxidant behavior, metal chelation, and free radical scavenging. This biopigment is of interest for biologically derived batteries and supercapacitors. In this work, we characterized the voltammetric properties of chemically controlled eumelanins produced from 5,6-dihydroxyindole (DHI) and 5,6-dihydroxyindole-2-carboxylic acid (DHICA) building blocks, namely, DHI-melanin, DHICA-melanin, and natural eumelanin, extracted from the ink sac of cuttlefish, Sepia melanin. Eumelanin electrodes were studied for their cyclic voltammetric properties in acidic buffers including Na⁺, K⁺, NH₄⁺, and Cu²⁺ ions. (C) 2017 Author(s)

Degradative actions of microbial xylanolytic activities on hemicelluloses from rhizome of Arundo donax

Polysaccharidases from extremophiles are remarkable for specific action, resistance to different reaction conditions and other biotechnologically interesting features. In this article the action of crude extracts of thermophilic microorganisms (Thermotoga neapolitana, Geobacillus thermantarcticus and Thermoanaerobacterium thermostercoris) is studied using as substrate hemicellulose from one of the most interesting biomass crops, the giant reed (Arundo donax L.). This biomass can be cultivated without competition and a huge amount of rhizomes remains in the soil at the end of cropping cycle (10–15 years) representing a further source of useful molecules. Optimization of the procedure for preparation of the hemicellulose fraction from rhizomes of Arundo donax, is studied. Polysaccharidases from crude extracts of thermophilic microorganisms revealed to be suitable for total degradative action and/or production of small useful oligosaccharides from hemicelluloses from A. donax. Xylobiose and interesting tetra- and pentasaccharide are obtained by enzymatic action in different conditions. Convenient amount of raw material was processed per mg of crude enzymes. Raw hemicelluloses and pretreated material show antioxidant activity unlike isolated tetra- and pentasaccharide. The body of results suggest that rhizomes represent a useful raw material for the production of valuable industrial products, thus allowing to increase the economic efficiency of A. donax cultivation

Adenine interaction with and adsorption on Fe-ZSM-5 zeolites: A prebiotic chemistry study using different techniques

Most adsorption experiments are performed under conditions that did not exist on Earth before the life arose on it. Because adsorption is the first step for all other processes (protection against degradation and polymerization), it is important that it is performed under conditions that existed on prebiotic Earth. In this paper, we use an artificial seawater (seawater 4.0 Ga), which contains major cations and anions that could present on the oceans of the prebiotic Earth. In addition, zeolites, with substituted Fe in the framework, and adenine were probably common substances on the prebiotic Earth. Thus, study the interaction between them is an important issue in prebiotic chemistry. There are two main findings described in this paper. Firstly, zeolites with different Si/Fe ratios adsorbed adenine differently. Secondly, XAFS showed that, after treatments with seawater 4.0 Ga and adenine, an increase in the complexity of the system occurred. In general, salts of seawater 4.0 Ga did not affect the adsorption of adenine onto zeolites and adenine adsorbed less onto zeolites with iron isomorphically substituted. The C=C and NH2 groups of adenine interacted with the zeolites. Gypsum, formed from aqueous species dissolved in seawater 4.0 Ga, precipitated onto zeolites. EPR spectra of zeolites showed lines caused by Fe framework and Fe3+ species. TG curves of zeolites showed events caused by loss of water weakly bound to zeolite (in the 30-140 °C range), water bounded to iron species or cations from seawater 4.0 Ga or located in the cavities of zeolites (157-268 °C) and degradation of adenine adsorbed onto zeolites (360-600 °C). Mass loss follows almost the same order as the amount of adenine adsorbed onto zeolites. The XAFS spectrum showed that Fe3+ could be substituted into the framework of the Fe7-ZSM-5 zeolite