Interactions of reactive sulfur species with metalloproteins.

Reactive sulfur species (RSS) entail a diverse family of sulfur derivatives that have emerged as important effector molecules in H2S-mediated biological events. RSS (including H2S) can exert their biological roles via widespread interactions with metalloproteins. Metalloproteins are essential components along the metabolic route of oxygen in the body, from the transport and storage of O2, through cellular respiration, to the maintenance of redox homeostasis by elimination of reactive oxygen species (ROS). Moreover, heme peroxidases contribute to immune defense by killing pathogens using oxygen-derived H2O2 as a precursor for stronger oxidants. Coordination and redox reactions with metal centers are primary means of RSS to alter fundamental cellular functions. In addition to RSS-mediated metalloprotein functions, the reduction of high-valent metal centers by RSS results in radical formation and opens the way for subsequent per- and polysulfide formation, which may have implications in cellular protection against oxidative stress and in redox signaling. Furthermore, recent findings pointed out the potential role of RSS as substrates for mitochondrial energy production and their cytoprotective capacity, with the involvement of metalloproteins. The current review summarizes the interactions of RSS with protein metal centers and their biological implications with special emphasis on mechanistic aspects, sulfide-mediated signaling, and pathophysiological consequences. A deeper understanding of the biological actions of reactive sulfur species on a molecular level is primordial in H2S-related drug development and the advancement of redox medicine.

Iodide Removal by Resorcinol-Formaldehyde Carbon Aerogels.

The adsorption technique is widely used in water purification, and its efficiency can be significantly improved by target-specific adsorbent design. Research on iodine and its ion removal from water has attracted a great deal of interest due to increased concentrations in the environment and acute toxic effects, e.g., in human thyroid cells. In this work, the iodide removal performance of two high-surface-area resorcinol-formaldehyde-based carbon aerogels was studied under acidic conditions. The BET surface area was 790 m2/g (RF_ac) and 375 m2/g (RMF-GO), with a corresponding micropore ratio of 36 and 26%, respectively. Both aerogels showed outstanding adsorption capacity, exceeding the reported performance of other carbons and Ag-doped materials. Owing to its basic nature, the RMF-GO carbon aerogel showed higher I- capacity, up to 97 mg/g, than the acidic RF_ac, which reached a capacity of 82 mg/g. The surface chemistry of the aerogels also played a distinct role in the removal. In terms of kinetics, RF_ac removed 60% of the iodide ions and RMF-GO 30% within 8 h. The removal kinetics was of the first order, with a half-life of 1.94 and 1.70 h, respectively.

Graphene Oxide Protected Copper Benzene-1,3,5-Tricarboxylate for Clean Energy Gas Adsorption.

Among microporous storage materials copper benzene-1,3,5-tricarboxylate (CuBTC MOF, Cu3(BTC)2 or HKUST-1) holds the greatest potential for clean energy gases. However, its usefulness is challenged by water vapor, either in the gas to be stored or in the environment. To determine the protection potential of graphene oxide (GO) HKUST1@GO composites containing 0-25% GO were synthesized and studied. In the highest concentration, GO was found to strongly affect HKUST-1 crystal growth in solvothermal conditions by increasing the pH of the reaction mixture. Otherwise, the GO content had practically no influence on the H2, CH4 and CO2 storage capacities, which were very similar to those from the findings of other groups. The water vapor resistance of a selected composite was compared to that of HKUST-1. Powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric (TG/DTG) and N2 adsorption techniques were used to monitor the changes in the crystal and pore structure. It was found that GO saves the copper-carboxyl coordination bonds by sacrificing the ester groups, formed during the solvothermal synthesis, between ethanol and the carboxyl groups on the GO sheets.