Transfer Events Research Articles

Catabolic pathway acquisition by rhizosphere bacteria readily enables growth with a root exudate component but does not affect root colonization.

Horizontal gene transfer (HGT) is a fundamental evolutionary process that plays a key role in bacterial evolution. The likelihood of a successful transfer event is expected to depend on the precise balance of costs and benefits resulting from pathway acquisition. Most experimental analyses of HGT have focused on phenotypes that have large fitness benefits under appropriate selective conditions, such as antibiotic resistance. However, many examples of HGT involve phenotypes that are predicted to provide smaller benefits, such as the ability to catabolize additional carbon sources. We have experimentally simulated the consequences of one such HGT event in the laboratory, studying the effects of transferring a pathway for catabolism of the plant-derived aromatic compound salicyl alcohol between rhizosphere isolates from the Pseudomonas genus. We find that pathway acquisition enables rapid catabolism of salicyl alcohol with only minor disruptions to the existing metabolic and regulatory networks of the new host. However, this new catabolic potential does not confer a measurable fitness advantage during competitive growth in the rhizosphere. We conclude that the phenotype of salicyl alcohol catabolism is readily transferable but is selectively neutral under environmentally relevant conditions. We propose that this condition is common and that HGT of many pathways will be self-limiting because the selective benefits are small.IMPORTANCEHorizontal gene transfer (HGT) is a key process in microbial evolution, but the factors limiting HGT are poorly understood. Aside from the rather unique scenario of antibiotic resistance, the evolutionary benefits of pathway acquisition are still unclear. To experimentally test the effects of pathway acquisition, we transferred a pathway for catabolism of a plant-derived aromatic compound between soil bacteria isolated from the roots of poplar trees and determined the resulting phenotypic and fitness effects. We found that pathway acquisition allowed bacteria to grow using the plant-derived compound in the laboratory, but that this new phenotype did not provide an advantage when the bacteria were reinoculated onto plant roots. These results suggest that the benefits of pathway acquisition may be small when measured under ecologically-relevant conditions. From an engineering perspective, efforts to alter microbial community composition in situ by manipulating catabolic pathways or nutrient availability will be challenging when gaining access to a new niche does not provide a benefit.

Intracellular gene transfer (IGT) events from the mitochondrial genome to the plastid genome of the subtribe ferulinae drude (Apiaceae) and their implications

BackgroundIntracellular gene transfer (IGT) is a phenomenon in genome evolution that occurs between the nuclear and organellar genomes of plants or between the genomes of different organelles. The majority of the plastid genomes (plastomes) in angiosperms have a conserved structure, but some species exhibit unexpected structural variations.ResultsIn this study, we focused on the Ferulinae, which includes Ferula, one of the largest genera in the Apiaceae family. We discovered IGTs in the rps12-trnV IGS region of the plastome’s inverted repeat (IR). We found that partial mitochondrial genome (mitogenome) sequences, ranging in length from about 2.8 to 5.8 kb, were imported into the plastome. In addition to these, that are known from other Scandiceae subtribes, the Ferulinae plastomes contained two unique mitogenome sequences. We have named these sequences Ferula Mitochondrial Plastid sequences (FeMP). FeMP1 varies in length from 336 bp to 1,100 bp, while FeMP2 ranges from 50 bp to 740 bp in length, with the exception of F. conocaula and F. kingdon-wardii, which do not possess FeMP2. Notably, FeMP2 includes a complete rps7 gene of mitogenome origin. In the maximum likelihood (ML) tree constructed from 79 protein-coding genes, Ferulinae appears as a monophyletic group, while Ferula shows paraphyly. Dorema and Fergania are nested within the Ferula clade, sharing the unusual characteristics of the Ferula plastome. Based on these findings, a reclassification of Dorema and Fergania is warranted.ConclusionsOur results shed light on the mechanism of plastome evolution in the Scandiceae with a focus on the unique plastome structure found in the Apiaceae. These findings enhance our understanding of the evolution of plant organellar genomes.

Classical Models of Hydroxide for Proton Hopping Simulations.

Hydronium (H3O+) and hydroxide (OH-) ions perform structural diffusion in water via sequential proton transfers ("Grotthuss hopping"). This phenomenon can be accounted for by interspersing stochastic proton transfer events in classical molecular dynamics simulations. The implementation of OH--mediated proton hopping is particularly challenging because classical force fields are known to produce overcoordinated solvation structures around the OH- ion. Here, we first explore the ability of two-particle point-charge models to reproduce both the solvation free energy and coordination number in TIP3P water. We find that this is possible only with unphysical changes in the nonbonded parameters which create problems in proton hopping simulations. We then construct a classical OH- model with the charge of oxygen distributed among three auxiliary particles. This model favors a lower coordination number by accepting three hydrogen bonds and weakly donating one. The model was implemented in the MOBHY module of the CHARMM program and was fit to reproduce the experimental aqueous diffusion coefficient of OH-. This parameterization gave reasonable electrophoretic mobilities and the expected accelerated transport under nanoconfinement.

Redox Noninnocent Copper(I) Complex Where Metal Is a Spectator and Ligand Is an Actor in the Glaser Coupling Reaction of Alkynes.

An extended trisazo dipyridyl ligand, L, and its copper(I) complex, [1]+, were synthesized and fully characterized. Complex [1]+ has five coordination geometry satisfied by ligand L. L has a low-lying π* orbital; thus, [1]+ showed very facile multiple ligand-based redox events. Moreover, due to the strong π-acceptor nature of L, the Cu(II)/Cu(I) redox potential of [1]+ was anodic (0.62 V). The redox events of both L and [1]+ were characterized using various spectroscopic studies and density functional theory (DFT) calculations. Taking advantage of the multiple facile ligand-based reductions in [1]+, the Glaser coupling reaction of terminal alkynes was explored. Various kinds of alkynes were found to be effective when using [1]+ as a precatalyst. The mechanism of the reaction was investigated thoroughly by several controlled experiments, isolation, and characterization of the intermediates using various spectroscopic studies as well as by single-crystal X-ray structure determination. These studies showed that the L in [1]+ acted not only in the electron transfer events but also as a locus for binding the substrate, breaking and forming bonds, and, finally, releasing the product. Thus, here, the metal mainly acted as a spectator and ligand L acted as an actor.

Re-sensitization of imipenem-resistant Pseudomonas aeruginosa and restoration of cephalosporins susceptibility in Enterobacteriaceae by recombinant Esterase B.

Sphingobium sp. SM42 Esterase B (EstB) is an enzyme with a dual function in degrading dibutyl phthalate (DBP) and catalyzing the cleavage of the C-S bond in C3-sidechains of the dihydrothiazine ring of cephalosporins, generating more active β-lactam derivatives. Global prokaryotic genome analysis revealed the existence of a gene identical to estB in Pseudomonas aeruginosa strain PS1 suggesting a horizontal gene transfer event involving estB. To investigate the effect of ectopic expression of EstB in the periplasm of Pseudomonas aeruginosa and several Enterobacteriaceae on antibiotic susceptibility levels, plasmid, pEstB, carrying a recombinant EstB fused with the signal peptide from Escherichia coli outer membrane protein A (OmpA) for periplasmic localization was constructed. The expression of EstB in the periplasm of P. aeruginosa and the Enterobacteriaceae: E. coli, Klebsiella pneumoniae, and Salmonella enterica serovar Typhi, increased susceptibility to carbapenems and cephalosporins. EstB reversed the imipenem resistance of P. aeruginosa ΔmexS and restored the changes in susceptibility to cephalosporins conferred by the downregulation of the outer membrane proteins, OmpK35 and OmpK36, in K. pneumoniae ΔramR-ompK36 to wild-type level. The introduction of EstB to the periplasmic space of Gram-negative bacteria can increase carbapenem and cephalosporin susceptibility.

Genome sequencing and comparative genomic analysis of bovine mastitis-associated non-aureus staphylococci and mammaliicocci (NASM) strains from India

We describe the whole-genome sequencing and comparative genomic analysis of 22 mastitis-associated NASM strains isolated from India. The mean genome size of the strains was 2.55 Mbp, with an average GC content of 32.2%. We identified 14 different sequence types (STs) among the 22 NASM strains. Of these, ST1 and ST6 of S. chromogenes were exclusively associated with bovine mastitis. Genome-wide SNP-based minimum spanning tree revealed the intricate phylogenetic relationships among NASM strains from India, categorizing them into five major clades. Interestingly, mastitis-associated strains formed separate subclades in all the NASM species studied, indicating distinct host-specific co-evolution. The study identified 32 antimicrobial resistance (AMR) genes and 53 virulence-associated genes, providing insights into the genetic factors that could contribute to the pathogenicity of NASM species. Some virulence and AMR genes were found in the predicted genomic islands, suggesting possible horizontal transfer events.

Evolution of g-type lysozymes in metazoa: insights into immunity and digestive adaptations.

Exploring the evolutionary dynamics of lysozymes is critical for advancing our knowledge of adaptations in immune and digestive systems. Here, we characterize the distribution of a unique class of lysozymes known as g-type, which hydrolyze key components of bacterial cell walls. Notably, ctenophores, and choanoflagellates (the sister group of Metazoa), lack g-type lysozymes. We reveal a mosaic distribution of these genes, particularly within lophotrochozoans/spiralians, suggesting the horizontal gene transfer events from predatory myxobacteria played a role in their acquisition, enabling specialized dietary and defensive adaptations. We further identify two major groups of g-type lysozymes based on their widespread distribution in gastropods. Despite their sequence diversity, these lysozymes maintain conserved structural integrity that is crucial for enzymatic activity, underscoring independent evolutionary pathways where g-type lysozymes have developed functionalities typically associated with different lysozyme types in other species. Specifically, using Aplysia californica as a reference species, we identified three distinct g-type lysozyme genes: two are expressed in organs linked to both feeding and defense, and the third exhibits broader distribution, likely associated with immune functions. These findings advance our understanding of the evolutionary dynamics shaping the recruitment and mosaic functional diversification of these enzymes across metazoans, offering new insights into ecological physiology and physiological evolution as emerging fields.

Comparative genomic analysis uncovered phylogenetic diversity, evolution of virulence factors, and horizontal gene transfer events in tomato bacterial spot Xanthomonas euvesicatoria.

Bacterial spot, caused by diverse xanthomonads classified into four lineages within three species, poses a significant threat to global pepper and tomato production. In Taiwan, tomato bacterial spot xanthomonads phylogenetically related to an atypical Xanthomonas euvesicatoria pv. perforans (Xep) strain NI1 from Nigeria were found. To investigate the genetic structure of Taiwanese Xep strains and determine the phylogenetic position of the atypical strains, we completed high-quality, gap-free, circularized genomes of seven Taiwanese Xep strains and performed comparative genomic analyses with genomes of X. euvesicatoria pathovars. Average nucleotide identity, core genome analysis, and phylogenomic analysis were conducted. Three sequenced strains were identified as typical Xep, while four clustered with the atypical strain NI1, forming a distinct genomovar within X. euvesicatoria, proposed as X. euvesicatoria genomovar taiwanensis (Xet). This new lineage likely originated in Taiwan and spread to Nigeria through global seed trade. At the genomovar level, chromosomes remained conserved among Taiwanese strains, while plasmids likely contributed to bacterial virulence, avirulence, and field fitness. Gap-free genomes revealed associations between the evolution of type III effectors, horizontal gene transfer events, plasmid diversity, and recombination. This study highlights the critical roles of horizontal gene transfer and plasmids in shaping the genetic makeup, evolution, and environmental adaptation of plant pathogenic xanthomonads. The identification of a new genomovar, X. euvesicatoria genomovar taiwanensis, provides insights into the diversity and global spread of bacterial spot pathogens through seed trade.

Detection of plasmids in Salmonella from poultry and investigating the potential horizontal transfer of antimicrobial resistance and virulence genes: PLASMID TRANSFER OF RESISTANCE AND VIRULENCE.

Antimicrobial resistance genes (ARGs) and virulence genes (VGs) have been widely reported in Salmonella which are major foodborne pathogens from poultry. This study assessed the replicon typing and conjugative ability of plasmids from poultry-derived Salmonella as well as ARGs and VGs carried by these plasmids using an in silico approach. Both PlasmidFinder 2.1 and VRprofile2 were employed to detect plasmids in Salmonella sequences downloaded from the National Center for Biotechnology Information (NCBI) Reference Sequences (RefSeq) database, and then oriTfinder was used to determine the conjugative ability of plasmids. The ARGs and VGs on plasmids were identified by both VRprofile2 and oriTfinder. The phenotypes of ARGs were predicted by ResFinder 4.1 and oriTfinder, while the phenotypes of virulence were predicted by oriTfinder and VRprofile2. We identified 183 plasmid sequences from 309 downloaded sequences. Among them, 77 (42.1 %) plasmids were conjugative, 25 (13.7 %) mobilizable, and 81 (44.3 %) non-mobilizable. Fifty-one plasmids (27.9 %) contained multi-replicons. One hundred and five plasmids carried 58 ARGs, belonging to 12 classes. The most prevalent ARG groups in plasmids were the aminoglycoside, β-lactam, sulfonamide, and tetracycline groups. In addition, 49 plasmids carried 36 different VGs belonging to 13 gene classes. The most prevalent VG groups were the adhesin, type III secretion system, and resistance to complement killing groups. The detected high percentage of conjugative plasmids and existence of many multiple replicons suggest possible high rates of plasmid-mediated horizontal gene transfer (HGT) events. Detection of previously unreported plasmid-borne VG (fdeC) from Salmonella in poultry calls for more vigilant monitoring.

Evolutionary genomics of the emergence of brown algae as key components of coastal ecosystems

Brown seaweeds are keystone species of coastal ecosystems, often forming extensive underwater forests, and are under considerable threat from climate change. In this study, analysis of multiple genomes has provided insights across the entire evolutionary history of this lineage, from initial emergence, through later diversification of the brown algal orders, down to microevolutionary events at the genus level. Emergence of the brown algal lineage was associated with a marked gain of new orthologous gene families, enhanced protein domain rearrangement, increased horizontal gene transfer events, and the acquisition of novel signaling molecules and key metabolic pathways, the latter notably related to biosynthesis of the alginate-based extracellular matrix, and halogen and phlorotannin biosynthesis. We show that brown algal genome diversification is tightly linked to phenotypic divergence, including changes in life cycle strategy and zoid flagellar structure. The study also showed that integration of large viral genomes has had a significant impact on brown algal genome content throughout the emergence of the lineage.

Ethylene and epoxyethane metabolism in methanotrophic bacteria: comparative genomics and physiological studies using Methylohalobius crimeensis.

The genome of the methanotrophic bacterium Methylohalobius crimeensis strain 10Ki contains a gene cluster that encodes a putative coenzyme-M (CoM)-dependent pathway for oxidation of epoxyethane, based on homology to genes in bacteria that grow on ethylene and propylene as sole substrates. An alkene monooxygenase was not detected in the M. crimeensis genome, so epoxyethane is likely produced from co-oxidation of ethylene by the methane monooxygenase enzyme. Similar gene clusters were detected in about 10% of available genomes from aerobic methanotrophic bacteria, primarily strains grown from rice paddies and other wetlands. The sparse occurrence of the gene cluster across distant phylogenetic groups suggests that multiple lateral gene transfer events have occurred in methanotrophs. In support of this, the gene cluster in M. crimeensis was detected within a large genomic island predicted using multiple methods. Growth studies, reverse transcription-quantitative PCR (RT-qPCR) and proteomics were performed to examine the expression of these genes in M. crimeensis. Growth and methane oxidation activity were completely inhibited by the addition of >0.5% (v/v) ethylene to the headspace of cultures, but at 0.125% and below, the inhibition was only partial, and ethylene was gradually oxidized. The etnE gene encoding epoxyalkane:CoM transferase was strongly upregulated in ethylene-exposed cells based on RT-qPCR. Proteomics analysis confirmed that EtnE and nine other proteins encoded in the same gene cluster became much more predominant after cells were exposed to ethylene. The results suggest that ethylene is strongly inhibitory to M. crimeensis, but the bacterium responds to ethylene exposure by expressing an epoxide oxidation system similar to that used by bacteria that grow on alkenes. In the obligate methanotroph M. crimeensis, this system does not facilitate growth on ethylene but likely alleviates toxicity of epoxyethane formed through ethylene co-oxidation by particulate methane monooxygenase. The presence of predicted epoxide detoxification systems in several other wetland methanotrophs suggests that co-oxidation of ambient ethylene presents a stress for methanotrophic bacteria in these environments and that epoxyethane removal has adaptive value.

Evaluating the gravitational wave detectability of globular clusters and the Magellanic Clouds for LISA

We used the stellar evolution code bpass and the gravitational wave (GW) simulation code legwork to simulate populations of compact binaries that may be detected by the future space-based GW detector LISA. Specifically, we simulate the Magellanic Clouds and binary populations mimicking several globular clusters, neglecting dynamical effects. We find that a handful of sources should be detectable in each of the Magellanic Clouds, but for globular clusters the amount of detectable sources will likely be less than one each. We compared our results to earlier research and find that our predicted numbers are several dozen times lower than both the results from calculations that used the stellar evolution code bse and take dynamical effects into account, and results from calculations that used the stellar evolution code SeBa for the Magellanic Clouds. Earlier research that compared bpass models for GW sources in the Galactic disk with bse models found a similarly sized discrepancy. We determine that this discrepancy is caused by differences between the stellar evolution codes, particularly in the treatment of mass transfer and common-envelope events in binaries: in bpass mass transfer is more likely to be stable and tends to lead to less orbital shrinkage in the common-envelope phase than in other codes. This difference results in fewer compact binaries with periods short enough to be detected by LISA existing in the bpass population. For globular clusters, we conclude that the impact of dynamical effects is uncertain based on the literature, but the differences in stellar evolution have an effect of a factor of 20 to 40 on the number of detectable binaries.

Genomic and transcriptomic perspectives on the origin and evolution of NUMTs in Orthoptera

Nuclear mitochondrial pseudogenes (NUMTs) result from the transfer of mitochondrial DNA (mtDNA) to the nuclear genome. NUMTs, as “frozen” snapshots of mitochondria, can provide insights into diversification patterns. In this study, we analyzed the origins and insertion frequency of NUMTs using genome assembly data from ten species in Orthoptera. We found divergences between NUMTs and contemporary mtDNA in Orthoptera ranging from 0 % to 23.78 %. The results showed that the number of NUMT insertions was significantly positively correlated with the content of transposable elements in the genome. We found that 39.09 %-68.65 % of the NUMTs flanking regions (2,000 bp) contained retrotransposons, and more NUMTs originated from mitochondrial rDNA regions. Based on the analysis of the mitochondrial transcriptome, we found a potential mechanism of NUMT integration: mitochondrial transcripts are reverse transcribed into double-stranded DNA and then integrated into the genome. The probability of this mechanism occurring accounts for 0.30 %-1.02 % of total mitochondrial nuclear transfer events. Finally, based on the phylogenetic tree constructed using NUMTs and contemporary mtDNA, we provide insights into ancient evolutionary events such as species-specific “autaponumts” and “synaponumts” shared among different species, as well as post-integration duplication events.

Global prevalence of Mycobacterium massiliense strains with recombinant rpoB genes (Rec-Mas) horizontally transferred from Mycobacterium abscessus: two major types, dominant circulating clone 7 and MLST ST46 sequence type.

Horizontal gene transfer (HGT) events play a pivotal role in the evolution of Mycobacterium abscessus into dominant circulating clones (DCCs), which is capable of causing patient-to-patient transmission. In particular, HGT of the rpoB gene between strains of different subspecies of M. abscessus could also compromise differentiation between strains of M. abscessus. Here, for the first time, using 1,786 M. abscessus genome sequences, we evaluated the global prevalence of M. abscessus strains subjected to rpoB HGT. We found a greater prevalence of M. abscessus subjected to rpoB HGT than to those subjected to hsp65 HGT, which is mainly due to two Rec-mas clones, dominant circulating clone 7 and ST46, which are responsible for dissemination between non-CF patients in Asia. Our data highlight the importance of rpoB HGT in the evolution of M. abscessus, particularly Mycobacterium massiliense, into virulent DCC clones.

Subgrid-scale model considering the inverse energy cascade using an artificial neural network

For the closure of the subgrid-scale (SGS) stress tensor, an artificial neural network (ANN)-based SGS model that takes account of the inverse energy cascade in isotropic turbulence is developed. The data required for training this ANN-based SGS model are provided by direct numerical simulation of isotropic turbulence with an inverse energy cascade. Two input features, the root mean square of the rate-of-strain tensor and the product of the eigenvalues of the rate-of-strain tensor, are employed to characterize the inverse energy cascade. An a priori test reveals that the ANN-based model adequately predicts the SGS stress tensor in the backward energy transfer process, and the predictive capability of the gradient model is found to be slightly poorer than that of the ANN-based model, while that of the Smagorinsky model is not satisfactory. In comparison with the gradient model, the ANN-based model even predicts a few backward energy transfer events in the stage of excessive energy dissipation. In addition, the off-diagonal component of the SGS stress tensor, rather than the diagonal component, may be intimately associated with the inverse energy cascade. The ANN-based SGS model presented here is expected to provide inspiration for future investigations of the construction of SGS models that take account of the inverse energy cascade.

Unveiling the Ultrafast Excitation Energy Transfer in Tetraarylpyrrolo[3,2-b]pyrrole-BODIPY Dyads.

We have synthesized two dyads (dyad 1 and 2) comprising of tetraarylpyrrolo[3,2-b]pyrrole (TAPP) and BODIPY. In dyad 1, two BODIPYs are directly connected with TAPP moiety whereas in dyad 2, BODIPYs are connected through phenylethynyl linkers. TAPP is a blue energy donor which is easy to synthesize and functionalize as compared to other well-known blue energy donors like pyrene, perylene etc. This is the first report of using TAPP as an energy donor in BODIPY based dyad molecules. Complete quenching of TAPP fluorescence in the dyads suggests fast energy transfer from TAPP to BODIPY unit (ETE~99.9 %). Ultrafast fluorescence and transient absorption spectroscopic studies of dyad 1 showed TAPP to BODIPY energy transfer in 125 fs (kET=8.0×1012 s-1) which is one of the fastest energy transfer events in BODIPY based dyad reported so far. Whereas, in dyad 2, energy transfer is almost four times slower (480 fs, kET=2.1×1012 s-1). These results were rationalized by theoretical Förster formulations. This study shows that suitably matched optical properties of TAPP and BODIPY dyes along with their easy syntheses will be the key to develop highly efficient energy transfer systems in future for multiple applications.

Construction of Spirocyclic Compounds via Electrochemical Intramolecular Dearomatization of Benzene Derivatives

AbstractThe spirocyclic framework is found in many natural products, some of which are biologically active. However, It remains a challenge to develop environmentally friendly and atom‐economic synthetic methods. Herein, we report an intramolecular dearomatization reaction of benzene derivatives enabled by electrochemistry‐mediated two successive single‐electron‐transfer (SET) processes, providing an alternative method for the rapid construction of spirocyclic skeletons without using sacrificial reagents. A series of cyclohexadiene products were obtained in 25–81% yields. Furthermore, a proposed mechanism involving a sequential electron transfer event was supported by cyclic voltammetry experiments. This strategy features transition‐metal‐free conditions and easy handling, which will greatly enhance its practical utility.

Determining the Axial Orientations of a Large Number of Flux Transfer Events Sequentially Observed by Cluster during a High-Latitude Magnetopause Crossing

Flux transfer events (FTEs) are magnetic structures generally believed to originate from time-varying magnetic reconnection at the Earth’s magnetopause. Despite years of research, the mechanism of how FTEs are formed through reconnection remains controversial. In various models, FTEs exhibit different global configurations. Studying the FTE axial orientation can provide insights into their global shape, thereby helping to distinguish the generation mechanisms. In this paper, taking advantage of the orbital characteristics of the four Cluster spacecraft, we devised a multi-spacecraft timing method to determine the axes of a total of 57 FTEs observed sequentially by Cluster during a high-latitude duskside magnetopause crossing. During the nearly five-hour observation, the interplanetary magnetic field (IMF) experienced a large rotation, leading to a substantial rotation of the magnetosheath magnetic field. The analysis results show two new features of the FTE axis that have not been reported before: (1) the axes of the FTEs gradually rotate in response to the turning of the IMF and the magnetosheath magnetic field; (2) the axes of the FTEs vary between the direction of the magnetosheath magnetic field and the direction of the reconnection X-line. These features indicate that FTEs may have a more complex global configuration than depicted by traditional FTE models.

Catalyst Protonation Changes the Mechanism of Electrochemical Hydride Transfer to CO2.

It is well-known that addition of a cationic functional group to a molecule lowers the necessary applied potential for an electron transfer (ET) event. This report studies the effect of a proton (a cation) on the mechanism of electrochemically driven hydride transfer (HT) catalysis. Protonated, air-stable [HFe4N(triethyl phosphine (PEt3))4(CO)8] (H4) was synthesized by reaction of PEt3 with [Fe4N(CO)12]- (A -) in tetrahydrofuran, with addition of benzoic acid to the reaction mixture. The reduction potential of H4 is -1.70 V vs SCE which is 350 mV anodic of the reduction potential for 4 -. Reactivity studies are consistent with HT to CO2 or to H+ (carbonic acid), as the chemical event following ET, when the electrocatalysis is performed under 1 atm of CO2 or N2, respectively. Taken together, the chemical and electrochemical studies of mechanism suggest an ECEC mechanism for the reduction of CO2 to formate or H+ to H2, promoted by H4. This stands in contrast to an ET, two chemical steps, followed by an ET (ECCE) mechanism that is promoted by the less electron rich catalyst A -, since A - must be reduced to A 2- before HA - can be accessed.

Comparative genomic analysis of Acanthamoeba from different sources and horizontal transfer events of antimicrobial resistance genes.

Acanthamoeba causes a serious blinding keratopathy, Acanthamoeba keratitis, which is currently under-recognized by clinicians. In this study, we analyzed 48 strains of Acanthamoeba using a whole-genome approach, revealing differences in pathogenicity and function between strains of different origins. Horizontal transfer events of antimicrobial resistance genes can help provide guidance as potential biomarkers for the treatment of specific Acanthamoeba keratitis cases.