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.

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.

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.

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.

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.

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.

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.

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.

Highly active electrolytes for rechargeable Mg batteries based on a [Mg2(µ-Cl)2](2+) cation complex in dimethoxyethane.

A novel [Mg2(µ-Cl)2](2+) cation complex, which is highly active for reversible Mg electrodeposition, was identified for the first time in this work. This complex was found to be present in electrolytes formulated in dimethoxyethane (DME) through dehalodimerization of non-nucleophilic MgCl2 by reacting with either Mg salts (such as Mg(TFSI)2, TFSI = bis(trifluoromethane)sulfonylimide) or Lewis acid salts (such as AlEtCl2 or AlCl3). The molecular structure of the cation complex was characterized by single crystal X-ray diffraction, Raman spectroscopy and NMR. The electrolyte synthesis process was studied and rational approaches for formulating highly active electrolytes were proposed. Through control of the anions, electrolytes with an efficiency close to 100%, a wide electrochemical window (up to 3.5 V) and a high ionic conductivity (>6 mS cm(-1)) were obtained. The understanding of electrolyte synthesis in DME developed in this work could bring significant opportunities for the rational formulation of electrolytes of the general formula [Mg2(µ-Cl)2][anion]x for practical Mg batteries.

A modular, energy-based approach to the development of nickel containing molecular electrocatalysts for hydrogen production and oxidation.

This review discusses the development of molecular electrocatalysts for H2 production and oxidation based on nickel. A modular approach is used in which the structure of the catalyst is divided into first, second, and outer coordination spheres. The first coordination sphere consists of the ligands bound directly to the metal center, and this coordination sphere can be used to control such factors as the presence or absence of vacant coordination sites, redox potentials, hydride donor abilities and other important thermodynamic parameters. The second coordination sphere includes functional groups such as pendent acids or bases that can interact with bound substrates such as H2 molecules and hydride ligands, but that do not form strong bonds with the metal center. These functional groups can play diverse roles such as assisting the heterolytic cleavage of H2, controlling intra- and intermolecular proton transfer reactions, and providing a physical pathway for coupling proton and electron transfer reactions. By controlling both the hydride donor ability of the catalysts using the first coordination sphere and the proton donor abilities of the functional groups in the second coordination sphere, catalysts can be designed that are biased toward H2 production, oxidation, or bidirectional (catalyzing both H2 oxidation and production). The outer coordination sphere is defined as that portion of the catalytic system that is beyond the second coordination sphere. This coordination sphere can assist in the delivery of protons and electrons to and from the catalytically active site, thereby adding another important avenue for controlling catalytic activity. Many features of these simple catalytic systems are good models for enzymes, and these simple systems provide insights into enzyme function and reactivity that may be difficult to probe in enzymes. This article is part of a Special Issue entitled: Metals in Bioenergetics and Biomimetics Systems.

Tumor antigen-specific CD4+ T cells in cancer immunity: from antigen identification to tumor prognosis and development of therapeutic strategies.

CD4(+) T cells comprise a large fraction of tumor infiltrating lymphocytes and it is now established that they may exert an important role in tumor immune-surveillance. Several CD4(+) T cell subsets [i.e. T helper (Th)1, Th2, T regulatory (Treg), Th17, Th22 and follicular T helper (Tfh)] have been described and differentiation of each subset depends on both the antigen presenting cells responsible for its activation and the cytokine environment present at the site of priming. Tumor antigen-specific CD4(+) T cells with different functional activity have been found in the blood of cancer patients and different CD4(+) T cell subsets have been identified at the tumor site by the expression of specific transcription factors and the profile of secreted cytokines. Importantly, depending on the subset, CD4(+) T cells may exert antitumor versus pro-tumor functions. Here we review the studies that first identified the presence of tumor-specific CD4(+) T cells in cancer patients, the techniques used to identify the tumor antigens recognized, the role of the different CD4(+) T cell subsets in tumor immunity and in cancer prognosis and the development of therapeutic strategies aimed at activating efficient antitumor CD4(+) T cell effectors.

Genistein induces apoptosis and autophagy in human breast MCF-7 cells by modulating the expression of proapoptotic factors and oxidative stress enzymes.

Breast cancer is one of the common tumors occurring in woman and despite treatment, the prognostic is poor. Genistein, a soy isoflavone, has been reported to have chemopreventive\chemotherapeutic potential in multiple tumor types. Here, we investigated the genistein antiproliferative effect in MCF-7 breast cancer, underlying the molecular mechanisms involved in this effect. MCF-7 cancer and CCD1059sK fibroblast cells were treated with estradiol (10 nM) or genistein (0.01-100 µM) for 24, 48, and 72 h and the cell proliferation was investigated by MTT; membrane cell permeability was evaluated by LDH and PI incorporation; apoptosis was investigated by externalization of phosphatidylserine by FACS; and presence of autophagy was detected by LC3A/B immunostaining. The expression of apoptotic proteins and antioxidant enzymes was evaluated by qPCR. The results demonstrate that genistein (100 µM) for 72 h of treatment selectively reduced MCF-7 cell proliferation independent of estrogen receptor activation, while no cytotoxicity was observed in fibroblast cells. Further experiments showed that genistein induced phosphatidylserine externalization and LC3A/B immunopositivity in MCF-7 cells, indicating apoptosis and autophagy cell death. Genistein increased in three times proapoptotic BAX/Bcl-2 ratio and promoted a parallel downregulation of 20 times of antiapoptotic survivin. In addition, genistein promoted a decrease of 5.5, 9.3, and 3.6 times of MnSOD, CuZnSOD, and TrxR mRNA expression, respectively, while the GPx expression was increased by 6.5 times. These results suggest that the antitumor effect of genistein involved the modulation of antioxidant enzyme and apoptotic signaling expression, which resulted in apoptosis and progression of autophagy.

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.

High catalytic rates for hydrogen production using nickel electrocatalysts with seven-membered cyclic diphosphine ligands containing one pendant amine.

A series of Ni-based electrocatalysts, [Ni(7P(Ph)2N(C6H4X))2](BF4)2, featuring seven-membered cyclic diphosphine ligands incorporating a single amine base, 1-para-X-phenyl-3,6-triphenyl-1-aza-3,6-diphosphacycloheptane (7P(Ph)2N(C6H4X), where X = OMe, Me, Br, Cl, or CF3), have been synthesized and characterized. X-ray diffraction studies have established that the [Ni(7P(Ph)2N(C6H4X))2](2+) complexes have a square planar geometry, with bonds to four phosphorus atoms of the two bidentate diphosphine ligands. Each of the complexes is an efficient electrocatalyst for hydrogen production at the potential of the Ni(II/I) couple, with turnover frequencies ranging from 2400 to 27,000 s(-1) with [(DMF)H](+) in acetonitrile. Addition of water (up to 1.0 M) accelerates the catalysis, giving turnover frequencies ranging from 4100 to 96,000 s(-1). Computational studies carried out on the [Ni(7P(Ph)2N(C6H4X))2](2+) family indicate the catalytic rates reach a maximum when the electron-donating character of X results in the pKa of the Ni(I) protonated pendant amine matching that of the acid used for proton delivery. Additionally, the fast catalytic rates for hydrogen production by the [Ni(7P(Ph)2N(C6H4X))2](2+) family relative to the analogous [Ni(P(Ph)2N(C6H4X)2)2](2+) family are attributed to preferred formation of endo protonated isomers with respect to the metal center in the former, which is essential to attain suitable proximity to the reduced metal center to generate H2. The results of this work highlight the importance of precise pKa matching with the acid for proton delivery to obtain optimal rates of catalysis.

Structural and spectroscopic characterization of 17- and 18-electron piano-stool complexes of chromium. Thermochemical analyses of weak Cr-H bonds.

The 17-electron radical CpCr(CO)(2)(IMe)(•) (IMe = 1,3-dimethylimidazol-2-ylidene) was synthesized by the reaction of IMe with [CpCr(CO)(3)](2), and characterized by single crystal X-ray diffraction and by electron paramagnetic resonance (EPR), IR, and variable temperature (1)H NMR spectroscopy. The metal-centered radical is monomeric under all conditions and exhibits Curie paramagnetic behavior in solution. An electrochemically reversible reduction to 18-electron CpCr(CO)(2)(IMe)(-) takes place at E(1/2) = -1.89(1) V vs Cp(2)Fe(+•/0) in MeCN, and was accomplished chemically with KC(8) in tetrahydrofuran (THF). The salts K(+)(18-crown-6)[CpCr(CO)(2)(IMe)](-)·½THF and K(+)[CpCr(CO)(2)(IMe)](-)·(3)/(4)THF were crystallographically characterized. Monomeric ion pairs are found in the former, whereas the latter has a polymeric structure because of a network of K···O((CO)) interactions. Protonation of K(+)(18-crown-6)[CpCr(CO)(2)(IMe)](-)·½THF gives the hydride CpCr(CO)(2)(IMe)H, which could not be isolated, but was characterized in solution; a pK(a) of 27.2(4) was determined in MeCN. A thermochemical analysis provides the Cr-H bond dissociation free energy (BDFE) for CpCr(CO)(2)(IMe)H in MeCN solution as 47.3(6) kcal mol(-1). This value is exceptionally low for a transition metal hydride, and implies that the reaction 2 [Cr-H] → 2 [Cr(•)] + H(2) is exergonic (ΔG = -9.0(8) kcal mol(-1)). This analysis explains the experimental observation that generated solutions of the hydride produce CpCr(CO)(2)(IMe)(•) (typically on the time scale of days). By contrast, CpCr(CO)(2)(PCy(3))H has a higher Cr-H BDFE (52.9(4) kcal mol(-1)), is more stable with respect to H(2) loss, and is isolable.

Evolution of locomotion in Anthropoidea: the semicircular canal evidence.

Our understanding of locomotor evolution in anthropoid primates has been limited to those taxa for which good postcranial fossil material and appropriate modern analogues are available. We report the results of an analysis of semicircular canal size variation in 16 fossil anthropoid species dating from the Late Eocene to the Late Miocene, and use these data to reconstruct evolutionary changes in locomotor adaptations in anthropoid primates over the last 35 Ma. Phylogenetically informed regression analyses of semicircular canal size reveal three important aspects of anthropoid locomotor evolution: (i) the earliest anthropoid primates engaged in relatively slow locomotor behaviours, suggesting that this was the basal anthropoid pattern; (ii) platyrrhines from the Miocene of South America were relatively agile compared with earlier anthropoids; and (iii) while the last common ancestor of cercopithecoids and hominoids likely was relatively slow like earlier stem catarrhines, the results suggest that the basal crown catarrhine may have been a relatively agile animal. The latter scenario would indicate that hominoids of the later Miocene secondarily derived their relatively slow locomotor repertoires.

Investigating the role of the outer-coordination sphere in [Ni(P(Ph)2N(Ph­R)2)2]2+ hydrogenase mimics.

A series of dipeptide substituted nickel complexes with the general formula, [Ni(P(Ph)(2)N(NNA-amino acid/ester)(2))(2)](BF(4))(2), have been synthesized and characterized (P(2)N(2) = 1,5-diaza-3,7-diphosphacyclooctane, and the dipeptide consists of the non-natural amino acid, 3-(4-aminophenyl)propionic acid (NNA), coupled to amino acid/esters = glutamic acid, alanine, lysine, and aspartic acid). Each of these complexes is an active electrocatalyst for H(2) production. The effects of the outer-coordination sphere on the catalytic activity for the production of H(2) were investigated; specifically, the impact of sterics, the ability of the side chain or backbone to protonate and the pK(a) values of the amino acid side chains were studied by varying the amino acids in the dipeptide. The catalytic rates of the different dipeptide substituted nickel complexes varied by over an order of magnitude. The amino acid derivatives display the fastest rates, while esterification of the terminal carboxylic acids and side chains resulted in a decrease in the catalytic rate by 50-70%, implicating a significant role of protonated sites in the outer-coordination sphere on catalytic activity. For both the amino acid and ester derivatives, the complexes with the largest substituents display the fastest rates, indicating that catalytic activity is not hindered by steric bulk. These studies demonstrate the significant contribution that the outer-coordination sphere can have in tuning the catalytic activity of small molecule hydrogenase mimics.

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.