Density functional theory calculations have been performed to calculate the one-electron redox potential for a series of oxoiron(IV) porphyrin complexes of the form [(TMP)Fe(IV)(O)(L)] (TMP = 5,10,15,20-tetramesitylporphyrinate). Different axial ligands were chosen (L = none, Im, ClO4(-), CH3CO2(-), Cl(-), F(-), SCH3(-)) in order to compare the results with recent electrochemical experiments. T...

A facile method is developed to prepare monodisperse silver nanoparticles in a much enhanced yield by adding a trace amount of Fe(3+) ions into the reaction of AgNO(3) with oleic acid and oleylamine. We propose that Fe(2+) ions speed up the nucleation and growth of silver nanoparticles due to the electron-transfer between Ag(+) and Fe(2+), in which Fe(2+) is from Fe(3+) reduced by oleylamine.

We demonstrate the redox potential calculation relative to the normal hydrogen electrode (NHE) in nonaqueous solution using a density functional theory-based molecular dynamics (DFT-MD) simulation. The calculation of the NHE in nonaqueous solution consists of two processes: the first step is the equilibrated simulation for a proton in nonaqueous solution to determine the space for inserting a p...

The ability of living systems to respond to stimuli and process information has encouraged scientists to develop integrated nanosystems displaying similar functions and capabilities. In this regard, biological pores have been a source of inspiration due to their exquisite control over the transport of ions within cells, a feature that ultimately plays a major role in multiple physiological proc...

Azurin from Pseudomonas aeruginosa is a small 128-residue, copper-containing protein. Its redox potential can be modified by mutating the protein. Free-energy calculations based on classical molecular-dynamics simulations of the protein and from mutants in aqueous solution at different pH values were used to compute relative redox potentials. The precision of the free-energy calculations with t...

The installation of ferrocene molecules within the wide-channel metal-organic framework (MOF) compound, NU-1000, and subsequent configuration of the modified MOF as thin-film coatings on electrodes renders the MOF electroactive in the vicinity of the ferrocenium/ferrocene (Fc(+)/Fc) redox potential due to redox hopping between anchored Fc(+/0) species. The observation of effective site-to-site ...

Pheomelanin has been implicated in the increased susceptibility to UV-induced melanoma for people with light skin and red hair. Recent studies identified a UV-independent pathway to melanoma carcinogenesis and implicated pheomelanin's pro-oxidant properties that act through the generation of reactive oxygen species and/or the depletion of cellular antioxidants. Here, we applied an electrochemic...

BACKGROUND In the picture of a laboratory evolution experiment, to improve the thermostability whilst maintaining the activity requires of suitable procedures to generate diversity in combination with robust high-throughput protocols. The current work describes how to achieve this goal by engineering ligninolytic oxidoreductases (a high-redox potential laccase -HRPL- and a versatile peroxidase,...

In tropical regions, different species of fiddler crabs coexist on the mangrove floor, which sometimes makes it difficult to define species-specific habitat by visual inspection. The aim of this study is to find key environmental parameters which affect the distribution of fiddler crabs and to determine the habitats in which each species was most abundant. Crabs were collected from 19 sites wit...

Combinatorial saturation mutagenesis -CSM- is a valuable tool for improving enzymatic properties from hot-spot residues discovered by directed enzyme evolution or performing semi-rational studies. CSM coupled to a reliable high-throughput screening assay -coefficient of variance below 10%- has been used to enhance turnover rates in the fungal laccase variant T2 from Myceliophthora thermophila. ...