Shifting from marine reserves to maritime zoning for conservation of Pacific bigeye tuna (Thunnus obesus).

Over 50% of the total bigeye tuna (BET) landed in the Western Central Pacific Ocean is caught incidentally in the purse seine fishery and sold for canning at prices less than US$2/kg. The remainder is landed in longline fisheries directed at BET and sold as fresh or frozen tuna at prices greater than US$10/kg. The combined fishing mortality by all gears will soon reduce the BET biomass in the Pacific Ocean to less than that capable of producing maximum sustainable yield.

"Wurster-type" ureas as redox-active receptors for anions.

Four redox-active receptors, 1-4, based on the incorporation of p-phenylenediamine(s) within a urea framework, were synthesized, and the affinities of two for a series of anions were quantified through UV-vis and NMR spectroscopic studies. The structure of 1 was confirmed by X-ray crystallography. For the oxoanions studied, complex stabilities approached 10(6) M(-1) in acetonitrile and decreased with the decreasing basicity of the anion (CH(3)COO(-) > C(6)H(5)COO(-) > H(2)PO(4)(-) > NO(2)(-) > NO(3)(-)).

Wurster's crowns: a comparative study of ortho- and para-phenylenediamine-containing macrocyclic receptors.

Two series of isomeric, redox-responsive azacrown ethers based on ortho- and para-phenylenediamine (Wurster's crowns) have been synthesized and their properties explored through 13C NMR spectroscopy, electrospray ionization mass spectrometry, cyclic voltammetry, and X-ray crystallography. These crowns display strong affinity for alkali metal cations while maintaining comparable selectivity profiles to the parent crown ethers from which they are derived. Like Wurster's reagent (N,N,N',N'-tetramethyl-p-phenylenediamine or para-TMPD), the para-Wurster's crowns undergo two reversible one-electron oxidations.

Biomass, size, and trophic status of top predators in the Pacific Ocean.

Fisheries have removed at least 50 million tons of tuna and other top-level predators from the Pacific Ocean pelagic ecosystem since 1950, leading to concerns about a catastrophic reduction in population biomass and the collapse of oceanic food chains. We analyzed all available data from Pacific tuna fisheries for 1950-2004 to provide comprehensive estimates of fishery impacts on population biomass and size structure. Current biomass ranges among species from 36 to 91% of the biomass predicted in the absence of fishing, a level consistent with or higher than standard fisheries management targets.

Electron transfer vs coordination chemistry: isomer-specific binding of HgII by an ortho-Wurster's thiacrown ether.

Isomeric p- and o-phenylenediamine-containing macrocyclic hosts (Wurster's thiacrown ethers L1 and L2, respectively) were prepared and studied as Hg(II) ionophores. The distinct electrochemical properties of the two hosts allowed for the formation of a coordination compound with the ortho-Wurster's thiacrown ether but not the para isomer. In the latter case, the Hg(II) ion served as an oxidant in an electron-transfer reaction with the host.

A theoretical investigation on the Wurster's crown analogue of 18-crown-6.

An ab initio, quantum mechanical study of the Wurster's crown analogue of 18-crown-6 and its interactions with the alkali metal cations are presented. This study explores methods for accurately treating large, electron-rich species while providing an understanding of the molecular behavior of a representative member of this class of crowns. The molecular geometries, binding energies, and binding enthalpies are evaluated with methods similar to those reported for the analysis of 18-crown-6 and its alkali metal complexes to facilitate direct comparison.

Wurster's thiacrown ethers: synthesis, properties, and Pt(II)-coordination chemistry.

Two isomeric redox-responsive azathiacrown ethers, based on p-phenylenediamine, have been synthesized in traditional crown (L1) and crownophane (L2) architectures. Each of these "Wurster's crowns" was designed to target the encapsulation of transition or heavy metal ions. The solid-state structures of these ligands show binding cavities defined by three exocyclic sulfur atoms and either a N donor atom (L1) or the electron-rich pi face of the phenylenediamine subunit (L2).

"ortho-Wurster's crowns": synthesis and properties of a novel phenylenediamine-based redox-active macrocyclic ligand.

A hybrid, macrocyclic structure based on o-phenylenediamine and a crown ether promotes an intimate mutual interaction with a bound potassium ion in the form of chelation by the redox-active moiety. A general synthetic method and properties are described for the first member of a new class of redox-active, lariat-type macrocycles called the "o-Wurster's crowns".

Lipophilic derivatives of cyclam as new inhibitors of tumor cell growth.

Two new lipophilic tetraazamacrocycles were prepared and, in contrast to non-lipophilic analogs, found to be potent inhibitors of tumor cell growth in vitro with IC50 values below 10 micromolar.

Eye-tracking measures and human performance in a vigilance task.

Background: Visual scanning is necessary for aviation safety and similar vigilance tasks, but little is known about its characteristics in such tasks, including possible changes with alertness and fatigue. We explored concurrent eye movements and human performance during a vigilance task designed to require frequent visual scanning. Effects of time and auditory stimuli were examined.