Low oxygen: A (tough) way of life for Okavango fishes.

Botswana's Okavango Delta is a World Heritage Site and biodiverse wilderness. In 2016-2018, following arrival of the annual flood of rainwater from Angola's highlands, and using continuous oxygen logging, we documented profound aquatic hypoxia that persisted for 3.5 to 5 months in the river channel. Within these periods, dissolved oxygen rarely exceeded 3 mg/L and dropped below 0.5 mg/L for up to two weeks at a time. Although these dissolved oxygen levels are low enough to qualify parts of the Delta as a dead zone, the region is a biodiversity hotspot, raising the question of how fish survive. In association with the hypoxia, histological samples, collected from native Oreochromis andersonii (threespot tilapia), Coptodon rendalli (redbreast tilapia), and Oreochromis macrochir (greenhead tilapia), exhibited widespread hepatic and splenic inflammation with marked granulocyte infiltration, melanomacrophage aggregates, and ceroid and hemosiderin accumulations. It is likely that direct tissue hypoxia and polycythemia-related iron deposition caused this pathology. We propose that Okavango cichlids respond to extended natural hypoxia by increasing erythrocyte production, but with significant health costs. Our findings highlight seasonal hypoxia as an important recurring stressor, which may limit fishery resilience in the Okavango as concurrent human impacts rise. Moreover, they illustrate how fish might respond to hypoxia elsewhere in the world, where dead zones are becoming more common.

Use of organic precursors and graphenes in the controlled synthesis of carbon-containing nanomaterials for energy storage and conversion.

The development of high-performance electrochemical energy storage and conversion devices, including supercapacitors, lithium-ion batteries, and fuel cells, is an important step on the road to alternative energy technologies. Carbon-containing nanomaterials (CCNMs), defined here as pure carbon materials and carbon/metal (oxide, hydroxide) hybrids with structural features on the nanometer scale, show potential application in such devices. Because of their pronounced electrochemical activity, high chemical and thermal stability and low cost, researchers are interested in CCNMs to serve as electrodes in energy-related devices. Various all-carbon materials are candidates for electrochemical energy storage and conversion devices. Furthermore, carbon-based hybrid materials, which consist of a carbon component with metal oxide- or metal hydroxide-based nanostructures, offer the opportunity to combine the attractive properties of these two components and tune the behavior of the resulting materials. As such, the design and synthesis of CCNMs provide an attractive route for the construction of high-performance electrode materials. Studies in these areas have revealed that both the composition and the fabrication protocol employed in preparing CCNMs influence the morphology and microstructure of the resulting material and its electrochemical performance. Consequently, researchers have developed several synthesis strategies, including hard-templated, soft-templated, and template-free synthesis of CCNMs. In this Account, we focus on recent advances in the controlled synthesis of such CCNMs and the potential of the resulting materials for energy storage or conversion applications. The Account is divided into four major categories based on the carbon precursor employed in the synthesis: low molecular weight organic or organometallic molecules, hyperbranched or cross-linked polymers consisting of aromatic subunits, self-assembling discotic molecules, and graphenes. In each case, we highlight representative examples of CCNMs with both new nanostructures and electrochemical performance suitable for energy storage or conversion applications. In addition, this Account provides an overall perspective on the current state of efforts aimed at the controlled synthesis of CCNMs and identifies some of the remaining challenges.

General approach to low-molecular-weight metallogelators via the coordination-induced gelation of an L-glutamate-based lipid.

A twin-tailed glutamate-based lipid with a pyridine headgroup was prepared in good yield using standard amide coupling and protection/deprotection chemistry. The resulting Lewis basic lipid gels a wide array of hydrocarbon solvents at a critical gelation concentration (C(g)) of 0.3 wt %. The gelation of more polar solvents, such as ethanol, THF, dichloromethane, and chloroform, occurs with a C(g) of between 2 and 5 wt %, demonstrating the importance of hydrogen bonding interactions in gel formation. The importance of hydrogen bonding in this system was also demonstrated by IR observation of the amide bands, which show a substantial shift upon gelation. Solutions of this new organogelator with concentrations below C(g) rapidly form gels upon the introduction of a wide variety of metal salts or complexes, providing a convenient general method for the preparation of metallogelators. Spectroscopic evidence suggests that the enhanced gelation seen in the metal-containing systems can be explained by a cross-linking of gel fibril aggregates similar to those formed by the unmetalated gelator.

Reversible oxidative addition and reductive elimination of fluorinated disulfides at gold(I) thiolate complexes: a new ligand exchange mechanism.

Reaction of HAuCl4 x 3 H2O with excess HSAr (Ar = C6F5 or C6F4H) in ethanol, followed by addition of [Et4N]Cl, produced [Et4N][Au(SAr)4] (Ar = C6F5 (1a) or C6F4H (1b)) as red crystalline solids in high yield. These complexes are rare examples of homoleptic gold(III) thiolate complexes. The crystal structures 1 show square planar geometry at the gold center with elongated Au-S bonds. Both complexes undergo reversible reductive elimination/oxidative addition processes in solution via thermal and photochemical pathways. Equilibrium constant and photostationary state measurements indicate that the relative importance of the two pathways depends on the nature of the aromatic groups. The metal-containing reductive elimination products, [Et4N][Au(SAr)2] (Ar = C6F5 (2a) or C6F4H (2b)), were confirmed by both independent synthesis and crystallographic characterization. Cross-reactions between either 1 or 2 and various disulfides led to ligand exchange via an addition-elimination process, a previously unknown reaction pathway for ligand exchange at gold(I) centers.

Metal-Ligand Bonding in Coinage Metal-Phosphine Complexes: The Synthesis and Structure of Some Low-Coordinate Silver(I)-Phosphine Complexes.

Reaction of AgBF(4) with 2 equiv of Ph(3)P in acetonitrile followed by recrystallization from dichloromethane/hexane yields the mixed phosphine-nitrile complex [(Ph(3)P)(2)AgNCCH(3)]BF(4) (I) as its dichloromethane solvate, I.0.5CH(2)Cl(2). This solvate crystallizes in the monoclinic space group C2/c with a = 22.928(5), b = 12.700(3), c = 25.156(5) Å, beta = 97.53(3) degrees, and Z = 8. The acetonitrile ligand in I is loosely bound to the metal center and easily lost, even in the solid state, without decomposition. Hence, recrystallization of dried samples of I.0.5CH(2)Cl(2) from CH(2)Cl(2)/hexane results in isolation of the novel low-coordinate phosphine complex [(Ph(3)P)(2)Ag]BF(4) (II). II crystallizes in the monoclinic space group C2/c with a = 21.733(9), b = 12.272(4), c = 24.356(9) Å, beta = 95.01(3) degrees, and Z = 8. In both cases, a weak interaction is present between a fluorine atom of the BF(4)(-) anion and the silver cation. However, these interactions appear to be essentially electrostatic rather than dative in nature, implying that I is best considered a three-coordinate silver complex and that II is a rare, structurally characterized example of a two-coordinate silver-phosphine complex. These solid-state geometric assignments are supported by (31)P NMR studies, which reveal a Ag-P coupling constant of 550 Hz for II, consistent with the presence of a linear two-coordinate complex in solution. The NMR data also indicate that the phosphine ligands are involved in exchange processes, which are accelerated by the presence of a donor solvent such as acetonitrile. Comparison of II with its gold analogue supports the previously stated concept that gold atoms are smaller than silver atoms. An analysis of 13 other isostructural pairs of silver and gold complexes culled from the crystallographic database lends further support to this concept.