A Monometallic Bis(cyaphido) Complex.

The first example of a bis(cyaphido) complex, trans-[Ru(dppe)2(C≡P)2], is described, unequivocally demonstrating the synthetic accessibility and stability of complexes that feature more than one cyaphido ligand. Synthesis is achieved from the precedent cation [Ru(dppe)2(C≡P)]+ via sequential coordination and desilylation of the phosphaalkyne Me3SiC≡P. The heteroleptic analogue trans-[Ru(dppe)2(C≡N)(C≡P)] is also prepared from the same cation and NaCN; both cyaphido complexes are structurally characterized, enabling the first direct comparison of cyaphide with cyanide, its isoelectronic and isolobal counterpart. This demonstrates an enhanced π-acidity for -C≡P over -C≡N, while computational studies reveal also a higher π-donor character for the cyaphido ligand.

Variation in the cranial osteology of the amphisbaenian genus Zygaspis based on high-resolution x-ray computed tomography.

Amphisbaenians are a specialized fossorial group of reptiles, having developed head-first burrowing, a specialized skull architecture, and an elongated body. This group is generally small-bodied, with some species possessing skulls only a few millimeters long. In this study, we used high-resolution x-ray computed tomography to compare the skulls of 15 specimens from seven of the eight species in the amphisbaenian genus Zygaspis (Zygaspis dolichomenta, Zygaspis ferox, Zygaspis quadrifrons, Zygaspis kafuensis, Zygaspis nigra, Zygaspis vandami, and Zygaspis violacea). Both interspecific and intraspecific variation, including asymmetry, is observed among the cranial bones of the specimens. There are unique morphological features on some cranial bones, including the premaxilla and ectopterygoid of Z. quadrifrons, the pterygoid and vomer of Z. kafuensis, and the extracolumella of Z. nigra. Sexual dimorphism has been previously reported for the species Z. quadrifrons and is observed here as well.

Superior Hypogastric Nerve Blockade for Uterine Artery Embolization: A Systematic Review.

Superior hypogastric nerve block (SHNB) has potential to reduce pain following uterine artery embolization (UAE). However, existing studies are limited by design, sample size, or conflicting results. A systematic review of the literature was performed. Outcomes included technical success, time to complete SHNB, time under fluoroscopy, procedure time, time to recovery, needle repositioning, same-day discharge, readmission, pain, analgesic consumption, and adverse events. Of 15 included studies, the same-day discharge rate was 98.8%, and readmission rate was 6.9%. The mean pain score was 3.4 in patients who received SHNB compared to 4.3 among controls. Of patients who received SHNB, 46.7% did not require further pain medication. Major adverse events occurred in 0.4% of patients. Early clinical studies suggest that SHNB appears to reduce pain and analgesic consumption in patients undergoing UAE. Additional randomized trials are needed to confirm these findings.

Giant dwarf crocodiles from the Miocene of Kenya and crocodylid faunal dynamics in the late Cenozoic of East Africa.

We describe two new osteolaemine crocodylids from the Early and early Middle Miocene of Kenya: Kinyang mabokoensis tax. nov. (Maboko, 15 Ma) and Kinyang tchernovi tax. nov. (Karungu and Loperot, 18 Ma). Additional material referable to Kinyang is known from Chianda and Moruorot. The skull was broad and dorsoventrally deep, and the genus can be diagnosed based on the combined presence of a partial overbite, a subdivided fossa for the lateral collateral ligament on the surangular, and a maxilla with no more than 13 alveoli. Phylogenetic analyses based on morphological and combined morphological and molecular data support a referral of Kinyang to Osteolaeminae, and morphological data alone put the new taxon at the base of Euthecodontini. Some Kinyang maxillae preserve blind pits on the medial caviconchal recess wall. Kinyang co-occurs with the osteolaemine Brochuchus at some localities, and together, they reinforce the phylogenetic disparity between early Neogene osteolaemine-dominated faunas and faunas dominated by crocodylines beginning in the Late Miocene in the Kenya Rift. The causes of this turnover remain unclear, though changes in prevailing vegetation resulting from tectonic and climatic drivers may provide a partial explanation.

Impact of Catheter Ablation on Stroke, Cognitive Decline and Dementia.

AF has been consistently associated with multiple forms of dementia, including idiopathic dementia. Outcomes after catheter ablation for AF are favourable and patients experience a better quality of life, arrhythmia-free survival, and lower rates of hospitalisation compared to patients treated with antiarrhythmic drugs. Catheter ablation is consistently associated with lower rates of stroke compared to AF management without ablation in large national and healthcare system databases. Multiple observational trials have shown that catheter ablation is also associated with a lower risk of cognitive decline, dementia and improved cognitive testing that can be explained through a variety of pathways. Long-term, adequately powered, randomised trials are required to define the role of catheter ablation in the management of AF as a means to lower the risk of cognitive decline, stroke and dementia.

A comparison of factors affecting the small-scale distribution of mercury from artisanal small-scale gold mining in a Zimbabwean stream system.

Artisanal small-scale gold mining (ASGM) operations use mercury liberally in the gold extraction process and account for approximately one quarter of the anthropogenic mercury consumption worldwide. ASGM activities are concentrated in many impoverished and poorly regulated countries such as Zimbabwe, resulting in a number of negative impacts to health and the environment. To examine levels of mercury contamination in one such geographic locality, sediment and tailing samples were collected in a heavily mined watershed in southern Zimbabwe from May-June 2015. Samples were collected from multiple points within the stream system, as well as from around six stamp mills and a single industrial mine in the watershed. GPS point location data were taken for mining operations and sampling sites to examine the spatial patterns of mercury concentration. Data were first analyzed using linear regression and development of a MARS model, followed by application of an ANCOVA model to assess the relationship among mercury concentrations and percent organic material, distance downstream, and distance from potential contamination source. Mercury concentrations within the study area ranged from 6 to 1541 µg/kg dw (mean 142 µg/kg dw). Analyses of mercury concentrations indicated a positive relationship with percent organic material but a negative relationship with distance downstream and distance from potential contamination source. Results from this study help elucidate the relationship between gold production and the spatial scale of mercury contamination in aquatic ecosystems in Africa. These data may lead to a better understanding of the relationship between mercury use and community health, which may aid both the local and global communities in regulating mercury contamination of the environment.

Formation of Reversible Solid Electrolyte Interface on Graphite Surface from Concentrated Electrolytes.

Li-ion batteries (LIB) have been successfully commercialized after the identification of ethylene-carbonate (EC)-containing electrolyte that can form a stable solid electrolyte interphase (SEI) on carbon anode surface to passivate further side reactions but still enable the transportation of the Li+ cation. These electrolytes are still utilized, with only minor changes, after three decades. However, the long-term cycling of LIB leads to continuous consumption of electrolyte and growth of SEI layer on the electrode surface, which limits the battery's life and performance. Herein, a new anode protection mechanism is reported in which, upon changing of the cell potential, the electrolyte components at the electrode-electrolyte interface reorganize reversibly to form a transient protective surface layers on the anode. This layer will disappear after the applied potential is removed so that no permanent SEI layer is required to protect the carbon anode. This phenomenon minimizes the need for a permanent SEI layer and prevents its continuous growth and therefore may lead to largely improved performance for LIBs.

Controlling Proton Delivery through Catalyst Structural Dynamics.

The fastest synthetic molecular catalysts for H2 production and oxidation emulate components of the active site of hydrogenases. The critical role of controlled structural dynamics is recognized for many enzymes, including hydrogenases, but is largely neglected in designing synthetic catalysts. Our results demonstrate the impact of controlling structural dynamics on H2 production rates for [Ni(PPh2 NC6H4R2 )2 ]2+ catalysts (R=n-hexyl, n-decyl, n-tetradecyl, n-octadecyl, phenyl, or cyclohexyl). The turnover frequencies correlate inversely with the rates of chair-boat ring inversion of the ligand, since this dynamic process governs protonation at either catalytically productive or non-productive sites. These results demonstrate that the dynamic processes involved in proton delivery can be controlled through modification of the outer coordination sphere, in a manner similar to the role of the protein architecture in many enzymes. As a design parameter, controlling structural dynamics can increase H2 production rates by three orders of magnitude with a minimal increase in overpotential.

Diffusible iodine-based contrast-enhanced computed tomography (diceCT): an emerging tool for rapid, high-resolution, 3-D imaging of metazoan soft tissues.

Morphologists have historically had to rely on destructive procedures to visualize the three-dimensional (3-D) anatomy of animals. More recently, however, non-destructive techniques have come to the forefront. These include X-ray computed tomography (CT), which has been used most commonly to examine the mineralized, hard-tissue anatomy of living and fossil metazoans. One relatively new and potentially transformative aspect of current CT-based research is the use of chemical agents to render visible, and differentiate between, soft-tissue structures in X-ray images. Specifically, iodine has emerged as one of the most widely used of these contrast agents among animal morphologists due to its ease of handling, cost effectiveness, and differential affinities for major types of soft tissues. The rapid adoption of iodine-based contrast agents has resulted in a proliferation of distinct specimen preparations and scanning parameter choices, as well as an increasing variety of imaging hardware and software preferences. Here we provide a critical review of the recent contributions to iodine-based, contrast-enhanced CT research to enable researchers just beginning to employ contrast enhancement to make sense of this complex new landscape of methodologies. We provide a detailed summary of recent case studies, assess factors that govern success at each step of the specimen storage, preparation, and imaging processes, and make recommendations for standardizing both techniques and reporting practices. Finally, we discuss potential cutting-edge applications of diffusible iodine-based contrast-enhanced computed tomography (diceCT) and the issues that must still be overcome to facilitate the broader adoption of diceCT going forward.

Experimental and Computational Mechanistic Studies Guiding the Rational Design of Molecular Electrocatalysts for Production and Oxidation of Hydrogen.

Understanding how to control the movement of protons and electrons is crucial to the design of fast, efficient electrocatalysts for H2 production and oxidation based on earth-abundant metals. Our work seeks to address fundamental questions about proton movement. We have demonstrated that incorporating a pendant amine functioning as a proton relay in the second coordination sphere of a metal complex helps proton mobility, resulting in faster and more energy-efficient catalysts. Proton-transfer reactions can be rate-limiting and are influenced by several factors, such as pKa values, steric effects, hydrogen bonding, and solvation/desolvation of the exogenous base and acid employed. The presence of multiple protonation sites introduces branching points along the catalytic cycle, making less productive pathways accessible or leading to the formation of stable off-cycle species. Using ligands with only one pendant amine mitigates this problem and results in catalysts with high rates for production of H2, although generally at higher overpotentials. For H2 oxidation catalysts, iron complexes with a high H2 binding affinity were developed. However, these iron complexes had a pKa mismatch between the protonated metal center and the protonated pendant amine, and consequently intramolecular proton movement was slow. Taken altogether, our results demonstrate the necessity of optimizing the entire catalytic cycle because optimization of a specific catalytic step can negatively influence another step and not necessarily lead to a better catalytic performance. We discuss a general procedure, based on thermodynamic arguments, which allows the simultaneous minimization of the free-energy change of each catalytic step, yielding a nearly flat free-energy surface, with no large barriers due to energy mismatches from either high- or low-energy intermediates.

Kinetic Analysis of Competitive Electrocatalytic Pathways: New Insights into Hydrogen Production with Nickel Electrocatalysts.

The hydrogen production electrocatalyst Ni(P(Ph)2N(Ph)2)2(2+) (1) is capable of traversing multiple electrocatalytic pathways. When using dimethylformamidium, DMF(H)(+), the mechanism of H2 formation by 1 changes from an ECEC to an EECC mechanism as the potential approaches the Ni(I/0) couple. Two electrochemical methods, current-potential analysis and foot-of-the-wave analysis (FOWA), were performed on 1 to measure detailed kinetics of the competing ECEC and EECC pathways. A sensitivity analysis was performed on the methods using digital simulations to understand their strengths and limitations. Chemical rate constants were significantly underestimated when not accounting for electron-transfer kinetics, even when electron transfer was fast enough to afford a reversible noncatalytic wave. The EECC pathway of 1 was faster than the ECEC pathway under all conditions studied. Buffered DMF:DMF(H)(+) mixtures afforded an increase in the catalytic rate constant (k(obs)) of the EECC pathway, but k(obs) for the ECEC pathway did not change when using buffered acid. Further kinetic analysis of the ECEC path revealed that base increases the rate of isomerization from exo-protonated Ni(0) isomers to the catalytically active endo-isomers, but decreases the rate of protonation of Ni(I). FOWA did not provide accurate rate constants, but FOWA was used to estimate the reduction potential of the previously undetected exo-protonated Ni(I) intermediate. Comparison of catalytic Tafel plots for 1 under different conditions reveals substantial inaccuracies in the turnover frequency at zero overpotential when the kinetic and thermodynamic effects of the conjugate base are not accounted for properly.

Investigating the role of chain and linker length on the catalytic activity of an H2 production catalyst containing a ß-hairpin peptide.

Building on our recent report of an active H2 production catalyst [Ni(PPh 2NProp-peptide)2]2+ (Prop = para-phenylpropionic acid, peptide (R10) = WIpPRWTGPR-NH2, p = D-proline and P2N = 1-aza-3,6-diphosphacycloheptane) that contains structured ß-hairpin peptides, here we investigate how H2 production is effected by: (1) the length of the hairpin (eight or ten residues) and (2) limiting the flexibility between the peptide and the core complex by altering the length of the linker: para-phenylpropionic acid (three carbons) or para-benzoic acid (one carbon). Reduction of the peptide chain length from ten to eight residues increases or maintains the catalytic current for H2 production for all complexes, suggesting a non-productive steric interaction at longer peptide lengths. While the structure of the hairpin appears largely intact for the complexes, NMR data are consistent with differences in dynamic behavior which may contribute to the observed differences in catalytic activity. Molecular dynamics simulations demonstrate that complexes with a one-carbon linker have the desired effect of restricting the motion of the hairpin relative to the complex; however, the catalytic currents are significantly reduced compared to complexes containing a three-carbon linker as a result of the electron withdrawing nature of the -COOH group. These results demonstrate the complexity and interrelated nature of the outer coordination sphere on catalysis.

Anion-Tunable Properties and Electrochemical Performance of Functionalized Ferrocene Compounds.

We report a series of ionically modified ferrocene compounds for hybrid lithium-organic non-aqueous redox flow batteries, based on the ferrocene/ferrocenium redox couple as the active catholyte material. Tetraalkylammonium ionic moieties were incorporated into the ferrocene structure, in order to enhance the solubility of the otherwise relatively insoluble ferrocene. The effect of various counter anions of the tetraalkylammonium ionized species appended to the ferrocene, such as bis(trifluoromethanesulfonyl)imide, hexafluorophosphate, perchlorate, tetrafluoroborate, and dicyanamide on the solubility of the ferrocene was investigated. The solution chemistry of the ferrocene species was studied, in order to understand the mechanism of solubility enhancement. Finally, the electrochemical performance of these ionized ferrocene species was evaluated and shown to have excellent cell efficiency and superior cycling stability.

Cerebral complexity preceded enlarged brain size and reduced olfactory bulbs in Old World monkeys.

Analysis of the only complete early cercopithecoid (Old World monkey) endocast currently known, that of 15-million-year (Myr)-old Victoriapithecus, reveals an unexpectedly small endocranial volume (ECV) relative to body size and a large olfactory bulb volume relative to ECV, similar to extant lemurs and Oligocene anthropoids. However, the Victoriapithecus brain has principal and arcuate sulci of the frontal lobe not seen in the stem catarrhine Aegyptopithecus, as well as a distinctive cercopithecoid pattern of gyrification, indicating that cerebral complexity preceded encephalization in cercopithecoids. Since larger ECVs, expanded frontal lobes, and reduced olfactory bulbs are already present in the 17- to 18-Myr-old ape Proconsul these features evolved independently in hominoids (apes) and cercopithecoids and much earlier in the former. Moreover, the order of encephalization and brain reorganization was apparently different in hominoids and cercopithecoids, showing that brain size and cerebral organization evolve independently.

Modelling and assessment of the impact of radiocesium and radiostrontium contamination in the Thermaikos Gulf, Greece.

A radiological model for (137)Cs and (90)Sr dispersion in the marine environment of the Thermaikos Gulf, Greece, and the river catchments draining into the Gulf, is presented. The model, developed and implemented within the MOIRA-PLUS decision support system, integrates appropriate site-specific information. The model's performance has been tested using the available empirical (137)Cs activity concentration data in abiotic and biotic components of the gulf since the Chernobyl accident. Further, this paper describes the results of a modelling exercise performed within the IAEA's EMRAS II international modelling programme to estimate the environmental sensitivity of this characteristic Mediterranean coastal marine environment following radioactive contamination. The radiation doses to humans after a single hypothetical instantaneous deposition of 1000 Bq m(-2), assuming that all of their food intake from the marine pathway comes from the local environment, were calculated. The obtained results are consistent with estimates from other models for different coastal marine environments in the frame of the above-mentioned EMRAS exercise.

Molecular electrocatalysts for oxidation of hydrogen using earth-abundant metals: shoving protons around with proton relays.

Sustainable, carbon-neutral energy is needed to supplant the worldwide reliance on fossil fuels in order to address the persistent problem of increasing emissions of CO2. Solar and wind energy are intermittent, highlighting the need to develop energy storage on a huge scale. Electrocatalysts provide a way to convert between electrical energy generated by renewable energy sources and chemical energy in the form of chemical bonds. Oxidation of hydrogen to give two electrons and two protons is carried out in fuel cells, but the typical catalyst is platinum, a precious metal of low earth abundance and high cost. In nature, hydrogenases based on iron or iron/nickel reversibly oxidize hydrogen with remarkable efficiencies and rates. Functional models of these enzymes have been synthesized with the goal of achieving electrocatalytic H2 oxidation using inexpensive, earth-abundant metals along with a key feature identified in the [FeFe]-hydrogenase: an amine base positioned near the metal. The diphosphine ligands P(R)2N(R')2 (1,5-diaza-3,7-diphosphacyclooctane with alkyl or aryl groups on the P and N atoms) are used as ligands in Ni, Fe, and Mn complexes. The pendant amines facilitate binding and heterolytic cleavage of H2, placing the hydride on the metal and the proton on the amine. The pendant amines also serve as proton relays, accelerating intramolecular and intermolecular proton transfers. Electrochemical oxidations and deprotonations by an exogeneous amine base lead to catalytic cycles for oxidation of H2 (1 atm) at room temperature for catalysts derived from [Ni(P(Cy)2N(R')2)2](2+), Cp(C6F5)Fe(P(tBu)2N(Bn)2)H, and MnH(P(Ph)2N(Bn)2)(bppm)(CO) [bppm = (PAr(F)2)2CH2]. In the oxidation of H2 catalyzed by [Ni(P(Cy)2N(R')2)2](2+), the initial product observed experimentally is a Ni(0) complex in which two of the pendant amines are protonated. Two different pathways can occur from this intermediate; deprotonation followed by oxidation occurs with a lower overpotential than the alternate pathway involving oxidation followed by deprotonation. The Mn cation [Mn(P(Ph)2N(Bn)2)(bppm)(CO)](+) mediates the rapid (>10(4) s(-1) at -95 °C), reversible heterolytic cleavage of H2. Obtaining the optimal benefit of pendant amines incorporated into the ligand requires that the pendant amine be properly positioned to interact with a M-H or M(H2) bond. In addition, ligands are ideally selected such that the hydride-acceptor ability of the metal and the basicity of a pendant are tuned to give low barriers for heterolytic cleavage of the H-H bond and subsequent proton transfer reactions. Using these principles allows the rational design of electrocatalysts for H2 oxidation using earth-abundant metals.

Peramorphic traits in the tokay gecko skull.

Traditionally, geckos have been conceived to exhibit paedomorphic features relative to other lizards (e.g., large eyes, less extensively ossified skulls, and amphicoelous and notochordal vertebrae). In contrast, peramorphosis has not been considered an important process in shaping their morphology. Here, we studied different sized specimens of Gekko gecko to document ontogenetic changes in cranial anatomy, especially near maturity. Comparison of this species with available descriptions of other geckos resulted in the identification of 14 cranial characteristics that are expressed more strongly with size increase. These characteristics become move evident in later stages of post-hatching development, especially near maturation, and are, therefore, attributed to peramorphosis (hyperossification). ACCTRAN and DELTRAN character optimizations were applied to these characters using a tree of 11 genera derived from a gekkotan molecular phylogeny. This analysis revealed that G. gecko expresses the majority of these putative peramorphic features near maturity, and that some of these features are also expressed in species closely related to G. gecko. The characters studied have the potential to be applied in future phylogenetic and taxonomic studies of this group of lizards.