Melanin: Nature's 4th bioorganic polymer.

The pigments known as the melanins are widely recognized for their responsibility in the coloration of human skin, eyes, hair, and minimising the harmful effects of solar ultraviolet radiation. But specialists are aware that the melanins are present in all living kingdoms, barring viruses, and have functionality that extends beyond neutralizing ionising radiation. The ubiquitous presence of melanin in almost all human organs, recognized in recent years, as well as the presence of melanin in organisms that are evolutionarily distant from each other, indicate the fundamental importance of this class of material for all life forms. In this review, we argue for the need to accept melanins as the fourth primordial class of biological polymers, along with nucleic acids, proteins and polysaccharides. We consistently compare the properties of these canonical biological polymers with the properties of melanin and highlight key features that fundamentally distinguish melanins, their function and its mysteries.

Signatures of pancake bonding in hydrated eumelanin.

Pancake bonding phenomenology is applied for the first time in a bioorganic system, the pigment eumelanin, via a hydration-induced decrease of the interplanar distance down to 3.19 Å. The observation explains the long-term inconsistency between electron paramagnetic resonance and muon spin relaxation data for eumelanin.

Infrared fingerprints of water collective dynamics indicate proton transport in biological systems.

Recent publications on spectroscopy of water layers in water bridge structures revealed a significant enhancement of the proton mobility and the dielectric contribution of translational vibrations of water molecules in the interfacial layers compared to bulk water. Herewith, the results of long-term studies of proton dynamics in solid-state acids have shown that proton mobility increases significantly with the predominance of hydronium, but not Zundel, cations in the aqueous phase. In the present work, in the light of these data, we reanalyzed our previously published results on broadband dielectric spectroscopy of bovine heart cytochrome c, bovine serum albumin, and the extracellular matrix and filaments of Shewanella oneidensis MR-1. We revealed that, just as in water bridges, an increase in electrical conductivity in these systems correlates with an increase in the dielectric contribution of water molecular translational vibrations. In addition, the appearance of spectral signatures of the hydronium cations was observed only in those cases when the system revealed noticeable electrical conductivity due to delocalized charge carriers.

Interfacial water morphology in hydrated melanin.

The importance of electrically functional biomaterials is increasing as researchers explore ways to utilise them in novel sensing capacities. It has been recognised that for many of these materials the state of hydration is a key parameter that can heavily affect the conductivity, particularly those that rely upon ionic or proton transport as a key mechanism. However, thus far little attention has been paid to the nature of the water morphology in the hydrated state and the concomitant ionic conductivity. Presented here is an inelastic neutron scattering (INS) experiment on hydrated eumelanin, a model bioelectronic material, in order to investigate its 'water morphology'. We develop a rigorous new methodology for performing hydration dependent INS experiments. We also model the eumelanin dry spectra with a minimalist approach whereas for higher hydration levels we are able to obtain difference spectra to extract out the water scattering signal. A key result is that the physi-sorbed water structure within eumelanin is dominated by interfacial water with the number of water layers between 3-5, and no bulk water. We also detect for the first time, the potential signatures for proton cations, most likely the Zundel ion, within a biopolymer/water system. These new signatures may be general for soft proton ionomer systems, if the systems are comprised of only interfacial water within their structure. The nature of the water morphology opens up new questions about the potential ionic charge transport mechanisms within hydrated bioelectronics materials.

Redox chemistry in the pigment eumelanin as a function of temperature using broadband dielectric spectroscopy.

Conductive biomolecular systems are investigated for their promise of new technologies. One biomolecular material that has garnered interest for device applications is eumelanin. Its unusual properties have led to its incorporation in a wide set of platforms including transistor devices and batteries. Much of eumelanin's conductive properties are due to a solid state redox comproportionation reaction. However, most of the work that has been done to demonstrate the role of the redox chemistry in eumelanin has been via control of eumelanin's hydration content with scant attention given to temperature dependent behavior. Here we demonstrate for the first time consistency between hydration and temperature effects for the comproportionation conductivity model utilizing dielectric spectroscopy, heat capacity measurements, frequency scaling phenomena and recognizing that activation energies in the range of ∼0.5 eV correspond to proton dissociation events. Our results demonstrate that biomolecular conductivity models should account for temperature and hydration effects coherently.

Observation of dielectric universalities in albumin, cytochrome C and Shewanella oneidensis MR-1 extracellular matrix.

The electrodynamics of metals is well understood within the Drude conductivity model; properties of insulators and semiconductors are governed by a gap in the electronic states. But there is a great variety of disordered materials that do not fall in these categories and still respond to external field in an amazingly uniform manner. At radiofrequencies delocalized charges yield a frequency-independent conductivity σ 1(ν) whose magnitude exponentially decreases while cooling. With increasing frequency, dispersionless conductivity starts to reveal a power-law dependence σ 1(ν)∝ν s with s < 1 caused by hopping charge carriers. At low temperatures, such Universal Dielectric Response can cross over to another universal regime with nearly constant loss ε″∝σ1/ν = const. The powerful research potential based on such universalities is widely used in condensed matter physics. Here we study the broad-band (1-1012 Hz) dielectric response of Shewanella oneidensis MR-1 extracellular matrix, cytochrome C and serum albumin. Applying concepts of condensed matter physics, we identify transport mechanisms and a number of energy, time, frequency, spatial and temperature scales in these biological objects, which can provide us with deeper insight into the protein dynamics.

[Interaction of surface-active base with fraction of membrane-bound Williams's protons].

In the process of mitochondrial respiratory H(+)-pumps functioning, the fraction membrane-bound protons (R-protons), which have an excess of free energy is formed. According to R.J. Williams this fraction is included as energy source in the reaction of ATP synthesis. Previously, in our laboratory was found the formation of this fraction was found in the mitochondria and on the outer surface of mitoplast. On the mitoslast model we strictly shown that non-equilibrium R-proton fraction is localized on the surface of the inner mitochondrial membrane. In this paper a surface-active compound--anion of 2,4,6-trichloro-3-pentadecylphenol (TCP-C15) is described, which selectively interacts with the R-protons fraction in mitochondria. A detailed description of the specific interaction of the TCP-C15 with R-protons fraction in mitochondria is presented. Moreover, in this work it was found that phosphate transport system reacts with the R-protons fraction in mitochondria and plays the role of the endogenous volume regulation system of this fraction. The results of experiments are discussed in the terms of a local coupling model of the phosphorylation mechanism.

Molecular mechanisms of transformation of SkQ mitotropic quinones and the search for new approaches to creation of selective free radical traps.

Features of the mechanism of action of positively charged benzoquinone derivatives (SkQ), which are the analogs of coenzyme Q (I), plastoquinone (II), and tocopherol (III), are discussed. It is usually considered that the main target of these compounds is mitochondria, where they accumulate due to the positive charge of the molecule. In the present work, it is shown with model systems that the reduced forms of compounds (I-III) under certain conditions can transform into electrically neutral cyclic zwitterions, which theoretically can escape from the matrix of energized mitochondria against the concentration gradient. A weak uncoupling effect of molecules I-III has been found on mitochondria. Its existence is in agreement with the abovementioned transformation of positively charged hydroquinones of type Ia-IIIa into electrically neutral molecules. The data obtained with model systems suggest that the target of SkQ hydroquinones as free radical traps may be not only mitochondria but also biochemical systems of the cytoplasm. Due to the presence of a large number of reactive oxygen species (ROS)-dependent signal systems in a cell, the functioning of cytoplasmic systems might be disturbed under the action of antioxidants. The problem of selective effect of antioxidants is discussed in detail in the present work, and a functional diagram of selective decrease of the "background level" of ROS based on differences in the intensity of background and "signal" ROS fluxes is considered.