Endonuclease III (EndoIII) is a DNA glycosylase that contains the [4Fe4S] cluster, which is essential for the protein to bind to damaged DNA in a process called base excision repair (BER). Here we propose that the change in the covalency of Fe–S bonds of the [4Fe4S] cluster caused by double-stranded (ds)-DNA binding is accompanied by a change in their strength, which is due to alterations of the electronic structure of the cluster. Micro-FTIR spectroscopy in the mid-IR region and FTIR spectroscopy in the far IR (450 and 300 cm⁻¹) were used independently to study the structural changes in EndoIII and the behavior of the [4Fe4S] cluster it contains, in the native form and upon its binding to ds-DNA. Structural changes in the DNA itself were also examined. The characteristics vibrational modes, corresponding to Fe–S (sulfide) and Fe–S (thiolate) bonds were identified in the cluster through far IR spectroscopy as well through quantum chemistry calculations. Based on the experimental results, these vibrational modes shift in their spectral positions caused by negatively charged DNA in the vicinity of the cluster. Modifications of the Fe–S bond lengths upon DNA binding, both of the Fe–S (sulfide) and Fe–S (thiolate) bonds in the [4Fe4S] cluster of EndoIII are responsible for the stabilization of the cluster towards higher oxidation state (3+), and hence its redox communication along the ds-DNA helix.

Bioelectrochemistry can be defined as a branch of Chemical Science concerned with electron-proton transfer and transport involving biomolecules, as well as electrode reactions of redox enzymes. The bioelectrochemical reactions and system have direct impact in biotechnological development, in medical devices designing, in the behavior of DNA-protein complexes, in green-energy and bioenergy concepts, and make it possible an understanding of metabolism of all living organisms (e.g. humans) where biomolecules are integral to health and proper functioning. In the last years, many researchers have dedicated itself to study different redox enzymes by using electrochemistry, aiming to understand their mechanisms and to develop promising bioanodes and biocathodes for biofuel cells as well as to develop biosensors and implantable bioelectronics devices. Inside this scope, this review try to introduce and contemplate some relevant topics for enzyme bioelectrochemistry, such as the immobilization of the enzymes at electrode surfaces, the electron transfer, the bioelectrocatalysis, and new techniques conjugated with electrochemistry vising understand the kinetics and thermodynamics of redox proteins. Furthermore, examples of recent approaches in designing biosensors and biofuel developed are presented.

A broad mass spectrometry technique with bioelectrochemical control provides new insight into the enzyme kinetics and mechanisms.

Biochars (BCs) are very versatile adsorbents, mainly, in the effectiveness of adsorption of organic and inorganic compounds in aqueous solutions. Here, the sugarcane biomass (SCB) was used to produce biochar at different carbonization times: 1, 2, 3, 4, and 5 h, denominated as BC1, BC2, BC3, BC4, and BC5, respectively. The superficial reactivity was studied with adsorption equilibrium experiments and kinetics models; Methylene Blue (MB) was used as adsorbate at different pH values, concentrations, and temperatures. In summary, the carbonization time provides the increase of superficial area, with exception of BC4, which decreased. Equilibrium studies showed inflection points and fluctuations with different initial dye concentration and temperature; SCB showed the best adsorption capacity compared to the BCs at the three temperatures tested, varying with the increase of MB concentration, suggesting the dependence of these two main factors on the adsorption process. The proposed adsorption mechanism suggests the major influence of Coulomb interactions, H-bonding, and π-interactions on the adsorption of MB onto adsorbents, evidencing that the adsorption is led by physical adsorption. Therefore, the results led to the use of the SCB without carbonization at 200 °C, saving energy and more adsorbent mass, considering that the carbonization influences weight loss. This study has provided insights of the use of SCB in MB dye adsorption as a low-cost and eco-friendly adsorbent.