Formic Acid Production Via Methane Peroxide Oxidation Over Oxalic Acid Activated Fe-MFI Catalysts

Topics in Catalysis - The process of synthesis of formic acid via partial peroxide oxidation of methane over Fe-MFI zeolites, as well as the influence of the catalyst activation by oxalic acid on...     

The proton iron-sulfur cluster environment of the [FeFe]-hydrogenase maturation protein HydF from Thermotoga neapolitana

[FeFe]-hydrogenases contain a complex [4Fe–4S]-2Fe cluster (H-cluster) and are able to efficiently reduce protons to H₂. Due to their potential exploitation for renewable energy production biotechnologies, significant efforts have been put into understanding the mechanisms driving the H-cluster assembly, which involves three conserved proteins. Among them, HydF works as scaffold upon which the H-cluster precursor is synthesized and carrier to deliver it to the hydrogenase, resulting in its activation. A FeS cluster binding sequence (CxHx₄₆-₅₃HCxxC) is conserved in all HydF proteins and should in principle provide four ligands to coordinate the Fe atom. However, we found that alternative metal coordination may exist in different HydF proteins and that only the three cysteines are strictly required, whereas the fourth ligand may vary and is, in any case, readily exchangeable. In this work we analyzed by EPR/HYSCORE the FeS cluster proton environment of HydF from Thermotoga neapolitana to determine the possible role of surrounding residues in the non-cysteinyl iron ligation of the protein.     

A signature protein-based method to distinguish Mediterranean water buffalo and foreign breed milk

A novel genetic variant at the α_s1-casein locus of water buffalo (WB), 8-residue shorter than its wild-type has been found and sequenced. The internal deletion of the peptide E³⁵KVNELsT⁴² was confirmed by the isolation of the junction peptide. The 8-residue deletion mutant has a molecular weight that is 919 Da less than that of the wild-type. The novel isoform with a unique f35-42 deletion could be the result of the skipping of exon 6, generating an exon 6-deleted variant of α_s1-casein. The wild-type and its shortened α_s1-casein forms were found to co-exist in many individual milk samples. In contrast, the 8-residue, internally deleted α_s1-casein variant did not occur in water buffaloes of the Mediterranean breed reared in Italy. Wild-type α_s1-casein has 6 to 8 phosphate groups (P) while the internally deleted form 6 and 7P per molecule.     

Structural Analysis of Partial and Total Esters of Glycerol Undecenoate and Diglycerol Undecenoate

The direct esterification reaction between glycerol and undecylenic acid or between diglycerol and undecylenic acid generates all the possible types of glycerol or diglycerol esters. Purification by silica gel chromatography resulted in the isolation of each of these types of ester in a pure form. The molecular structures of the compounds isolated were characterized and identified by mass spectrometry, ¹H NMR, ¹³C NMR and DEPT‐135. We then studied the composition of esters of undecylenic acid formed with glycerol or diglycerol as a function of their reaction conditions, which constitute a highly complex system. We purified undecylenic acid esters from each polyol family to allow the structural identification of each ester of glycerol and each ester of diglycerol with undecylenic acid. We found that the polarity of these non‐ionic amphiphilic esters directly affected their affinity for organic and inorganic solvents and that these esters behaved very differently from anionic amphiphilic molecules, such as undecylenic acid.     

Cast Iron Inoculation Enhanced by Supplementary Oxy-sulfides Forming Elements

Inoculation is one of the most important metallurgical treatments applied to the molten cast iron immediately prior to casting, to promote solidification without excessive eutectic undercooling, which favors carbides formation usually with undesirable graphite morphologies. The paper focused on the separate addition of an inoculant enhancer alloy [S, O, oxy-sulfides forming elements] with a conventional Ca-FeSi alloy, in the production of gray and ductile cast irons. Carbides formation tendency decreased with improved graphite characteristics as an effect of the [Ca-FeSi + Enhancer] inoculation combination, when compared to other Ca/Ca, Ba/Ca, RE-FeSi alloy treatments. Adding an inoculant enhancer greatly enhances inoculation, lowers inoculant consumption up to 50% or more and avoids the need to use more costly inoculants, such as a rare earth bearing alloy. The Inoculation Specific Factor [ISF] was developed as a means to more realistically measure inoculant treatment efficiency. It compares the ratio between the improved characteristic level and total inoculant consumption for this effect. Addition of any of the commercial inoculants plus the inoculant enhancer offered outstanding inoculation power [increased ISF] even at higher solidification cooling rates, even though the total enhancer addition was at a small fraction of the amount of commercial inoculant used.     

The History of ICRP and the Evolution of its Policies

Within 12 months of the discovery of X rays in 1895, papers appeared in the literature reporting adverse effects from high exposure. In 1925, the first International Congress of Radiology, held in London, considered the need for a protection committee, which it established at its second congress in Stockholm in 1928. This paper celebrates the 80^th anniversary of ICRP by tracing the history of the development of its policies, and identifying a few of the personalities involved from its inception up to the modern era. The paper follows the progress from the early controls on worker doses to avoid deterministic effects, through the identification of stochastic effects, to the concerns about public exposure and increasing stochastic risk estimates. The key features of the recommendations made by ICRP from 1928 up to the most recent in 2007 are identified.