Melanins are pigmentary macromolecules found throughout the biosphere that, in the 1970s, were discovered to conduct electricity and display bistable switching. Since then, it has been widely believed that melanins are naturally occurring amorphous organic semiconductors. Here, we report electrical conductivity, muon spin relaxation, and electron paramagnetic resonance measurements of melanin as the environmental humidity is varied. We show that hydration of melanin shifts the comproportionation equilibrium so as to dope electrons and protons into the system. This equilibrium defines the relative proportions of hydroxyquinone, semiquinone, and quinone species in the macromolecule. As such, the mechanism explains why melanin at neutral pH only conducts when “wet” and suggests that both carriers play a role in the conductivity. Understanding that melanin is an electronic-ionic hybrid conductor rather than an amorphous organic semiconductor opens exciting possibilities for bioelectronic applications such as ion-to-electron transduction given its biocompatibility.

Inorganic semiconductors permeate virtually every sphere of modern human existence. Micro-fabricated memory elements, processors, sensors, circuit elements, lasers, displays, detectors, etc are ubiquitous. However, the dawn of the 21st century has brought with it immense new challenges, and indeed opportunities-some of which require a paradigm shift in the way we think about resource use and disposal, which in turn directly impacts our ongoing relationship with inorganic semiconductors such as silicon and gallium arsenide. Furthermore, advances in fields such as nano-medicine and bioelectronics, and the impending revolution of the 'ubiquitous sensor network', all require new functional materials which are bio-compatible, cheap, have minimal embedded manufacturing energy plus extremely low power consumption, and are mechanically robust and flexible for integration with tissues, building structures, fabrics and all manner of hosts. In this short review article we summarize current progress in creating materials with such properties. We focus primarily on organic and bio-organic electronic and optoelectronic systems derived from or inspired by nature, and outline the complex charge transport and photo-physics which control their behaviour. We also introduce the concept of electrical devices based upon ion or proton flow ('ionics and protonics') and focus particularly on their role as a signal interface with biological systems. Finally, we highlight recent advances in creating working devices, some of which have bio-inspired architectures, and summarize the current issues, challenges and potential solutions. This is a rich new playground for the modern materials physicist.

We demonstrate experimentally for the first time the presence of two free radicals in the pigment eumelanin.

Today, western society is facing challenges to create new medical technologies to service an aging population as well as the ever-increasing e-waste of electronic devices and sensors. A key solution to these challenges will be the use of biomaterials and biomimetic systems. One material that has been receiving serious attention for its biomedical and device applications is eumelanin. Eumelanin, or commonly known as melanin, is nature’s brown-black pigment and is a poly-indolequinone biopolymer, which possess unique physical and chemical properties for material applications. Presented here is a review, aimed at polymer and other materials scientists, to introduce eumelanin as a potential material for research. Covered here are the chemical and physical structures of melanin, an overview of its unique physical and chemical properties, as well as a wide array of applications, but with an emphasis on device and sensing applications. The review is then finished by introducing interested readers to novel synthetic protocols and post synthesis fabrication techniques to enable a starting point for polymer research in this intriguing and complex material.

The first all solid state organic electrochemical transistor based upon the skin pigment melanin.