Rapid Water Reduction to H_2 Catalyzed by a Cobalt Bis(iminopyridine) Complex

A cobalt bis(iminopyridine) complex is a highly active electrocatalyst for water reduction, with an estimated apparent second order rate constant k_(app) ≤ 10^7 M^(–1)s^(–1) over a range of buffer/salt concentrations. Scan rate dependence data are consistent with freely diffusing electroactive species over pH 4–9 at room temperature for each of two catalytic reduction events, one of which is believed to be ligand based. Faradaic H_2 yields up to 87 ± 10% measured in constant potential electrolyses (−1.4 V vs SCE) confirm high reactivity and high fidelity in a catalyst supported by the noninnocent bis(iminopyridine) ligand. A mechanism involving initial reduction of Co^(2+) and subsequent protonation is proposed

Androgen Receptor and Vasopressin Receptor (AVPR1a) Genetic Polymorphisms are not associated with Marital Status or Fertility among Ariaal Men of Northern Kenya

A growing body of scholarship implicates testosterone and vasopressin in male reproductive behavior, including in humans. Since hormones exert their effects through their respective receptors, an open question has been whether genetic polymorphisms in the androgen receptor and vasopressin 1a receptor (AVPR1a) impact human male social behavior. Here, we sought to test for associations between polymorphisms in the coding region of the androgen receptor and promoter region of AVPR1a in relation to marital status and fertility among pastoralist Ariaal men of northern Kenya. None of the three polymorphisms were related to marital status (single, monogamously married, polygynously married) or fertility (number of current living children). We discuss these null findings in light of existing data

The effect of NOM characteristics and membrane type on microfiltration performance

Efforts to understand and predict the role of different organic fractions in the fouling of low-pressure membranes are presented. Preliminary experiments with an experimental apparatus that incorporates automatic backwashing and filtration over several days has shown that microfiltration of the hydrophilic fractions leads to rapid flux decline and the formation of a cake or gel layer, while the hydrophobic fractions show a steady flux decline and no obvious formation of a gel or cake layer. The addition of calcium to the weakly hydrophobic acid (WHA) fraction led to the formation of a gel layer from associations between components of the WHA. The dominant foulants were found to be the neutral and charged hydrophilic compounds, with hydrophobic and small pore size membranes being the most readily fouled. The findings suggest that surface analyses such as FTIR will preferentially identify hydrophilic compounds as the main foulants, as these components form a gel layer on the surface while the hydrophobic compounds adsorb within the membrane pores. Furthermore, coagulation pre-treatment is also likely to reduce fouling by reducing pore constriction rather than the formation of a gel layer, as coagulants remove the hydrophobic compounds to a large extent and very little of the hydrophilic neutral components

Groups 5 and 6 Terminal Hydrazido(2−) Complexes: N_β Substituent Effects on Ligand-to-Metal Charge-Transfer Energies and Oxidation States

Brightly colored terminal hydrazido(2−) (dme)MCl_3(NNR_2) (dme = 1,2-dimethoxyethane; M = Nb, Ta; R = alkyl, aryl) or (MeCN)WCl_4(NNR_2) complexes have been synthesized and characterized. Perturbing the electronic environment of the β (NR_2) nitrogen affects the energy of the lowest-energy charge-transfer (CT) transition in these complexes. For group 5 complexes, increasing the energy of the N_β lone pair decreases the ligand-to-metal CT (LMCT) energy, except for electron-rich niobium dialkylhydrazides, which pyramidalize N_β in order to reduce the overlap between the Nb═Nα π bond and the Nβ lone pair. For W complexes, increasing the energy of N_β eventually leads to reduction from formally [W^(VI)≡N–NR_2] with a hydrazido(2−) ligand to [W^(IV)═N═NR_2] with a neutral 1,1-diazene ligand. The photophysical properties of these complexes highlight the potential redox noninnocence of hydrazido ligands, which could lead to ligand- and/or metal-based redox chemistry in early transition metal derivatives

Suppression of Classical and Quantum Radiation Pressure Noise via Electro-Optic Feedback

We present theoretical results that demonstrate a new technique to be used to improve the sensitivity of thermal noise measurements: intra-cavity intensity stabilisation. It is demonstrated that electro-optic feedback can be used to reduce intra-cavity intensity fluctuations, and the consequent radiation pressure fluctuations, by a factor of two below the quantum noise limit. We show that this is achievable in the presence of large classical intensity fluctuations on the incident laser beam. The benefits of this scheme are a consequence of the sub-Poissonian intensity statistics of the field inside a feedback loop, and the quantum non-demolition nature of radiation pressure noise as a readout system for the intra-cavity intensity fluctuations.Comment: 4 pages, 1 figur