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Meiotic recombination between homologous chromosomes is vital for maximizing genetic variation among offspring. However, sex-determining regions are often rearranged and blocked from recombination. It remains unclear whether rearrangements or other mechanisms might be responsible for recombination suppression. Here, we uncover that the deficiency of the DNA cytosine methyltransferase DNMT1 in the green algaChlamydomonas reinhardtiicauses anomalous meiotic recombination at the mating-type locus (MT), generating haploid progeny containing bothplusandminusmating-type markers due to crossovers withinMT. The deficiency of a histone methyltransferase for H3K9 methylation does not lead to anomalous recombination. These findings suggest that DNA methylation, rather than rearrangements or histone methylation, suppresses meiotic recombination, revealing an unappreciated biological function for DNA methylation in eukaryotes. 

Microkinetic models based on parameters obtained from density functional theory and transition state theory have been developed for the hydrodeoxygenation (HDO) of propanoic acid, a model lignocellulosic biomass-derived organic acid, over the flat Pd(100) and Pd(111) surfaces in both vapor and liquid phase reaction conditions. The more open Pd(100) surface was found to be 3–7 orders of magnitude more active than the Pd(111) surface in all reaction environments, indicating that the (111) surface is not catalytically active for the HDO of propanoic acid. Over Pd(100) and in vapor phase, liquid water, and liquid 1,4-dioxane, propanoic acid hydrodeoxygenation follows a decarbonylation (DCN) mechanism that is facilitated by initial α- and β-carbon dehydrogenation steps, prior to the rate controlling C–OH and (partially rate controlling) C–CO bond dissociations. Only over Pd(111) and aqueous reaction environments is the decarboxylation (DCX) preferred over the DCN with the C–CO 2 step being rate controlling. 

Deoxydehydration (DODH) is an emerging biomass deoxygenation process whereby vicinal OH groups are removed. Based on DFT calculations and microkinetic modeling, we seek to understand the mechanism of the Re-catalyzed deoxydehydration supported on CeO 2 (111). In addition, we aim at understanding the promotional effect of Pd in a heterogeneous ReO x –Pd/CeO 2 DODH catalyst system. We disentangle the contribution of the oxide support, the oxide-supported single ReO x species, and a co-adsorbed Pd promoter that has no direct interaction with the Re species. In the absence of a nearby Pd cluster, a Re site is able to reduce subsurface Ce-ions of a hydroxylated CeO 2 (111) surface, leading to a catalytically active Re +6 species. The effect of Pd is twofold: (i) Pd catalyzes the hydrogen dissociation and spillover onto CeO 2 , which is an indispensable process for the regeneration of the Re catalyst, and (ii) Pd adsorbed in close proximity to Re on CeO 2 (111) facilitates the oxidation of Re to a +7 oxidation state, which leads to an even more active Re species than the Re +6 site present in the absence of Pd. The latter promotional effect of Pd (and change in oxidation state of Re) disappears with increasing Pd–Re distance and in the presence of oxygen defects on the ceria support. Under these conditions, the ReO x –Pd/CeO 2 catalyst system exhibits appreciable activity consistent with recent experiments. The established mechanism and role of various species in the catalyst system help to better understand the deoxydehydration catalysis. Also, the importance of the Re oxidation state and the identified oxidation state modification mechanisms suggest a new pathway for tuning the properties of metal-oxide supported catalysts.