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. Closure of the high-seas enclaves in 2009 was hailed as a conservation measure, but was not scientifically evaluated before implementation and appears to have had no beneficial effect on the BET stock. A spatially explicit age-structured ecosystem model, SEAPODYM, is used to simulate alternative area-based fishery management policies to conserve bigeye tuna in the Western Central Pacific Ocean. Closing the high-seas enclaves to purse seine fishing has negligible effect on the BET biomass. Fishery management policies that control mortality on both juveniles and adults, through prohibition of fish aggregation devices in the purse seine fishery and restrictions on longline fishing in spawning areas, are the most efficient conservation policies. Large-scale benefits from bigeye conservation measures will become apparent only in the 2030s, assuming timely implementation and minimal effects of climate change.

"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)(-)). The presence of the urea functionality caused an increase in the oxidation potential of the p-phenylenediamine subunit compared to that of free p-phenylenediamine. Electrochemical studies of the anion complexes revealed two-wave behavior with the appearance of a second oxidation wave cathodic to that in the free receptors and characteristic of the bound anion. Ab initio DFT studies of a representative acetate complex revealed the consequences of host oxidation state on complex structure.

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. The integrity of the alkali metal ion complexes is maintained in the neutral and singly oxidized ligand states but not after removal of two electrons. In contrast, the oxidation of ortho-Wurster's crowns is scan rate dependent, occurring at potentials substantially higher than their para counterparts, with their complexes oxidizing irreversibly. X-ray crystal structures of representative complexes show, in all cases, participation of the redox-active phenylenediamine subunits in complex formation via direct bonding to the guest cation.

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. Fish larger than 175 centimeters fork length have decreased from 5% to approximately 1% of the total population. The trophic level of the catch has decreased slightly, but there is no detectable decrease in the trophic level of the population. These results indicate substantial, though not catastrophic, impacts of fisheries on these top-level predators and minor impacts on the ecosystem in the Pacific Ocean.

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. Solutions of the Hg(II) complex of L2 were studied by 13C NMR spectroscopy and cyclic voltammetry and revealed a strong interaction between the redox-active phenylenediamine subunit and the bound metal cation. An X-ray analysis confirmed the participation of the three macrocyclic S atoms and both phenylenediamine N atoms in the stabilization of the complex.

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. Hybrid density functional methods are applied to gauge the effects of electron correlation on the geometries of the electron-rich phenylenediamine moiety present in the Wurster's crowns. While the structure of the crown ether backbone is largely unperturbed by the incorporation of the redox active functionality, the alkali metal binding enthalpies are uniformly stronger for the Wurster's crown complexes, adding 1.8 to 5.1 kcal/mol to the strength of the interaction, depending on cation type. The additional strength, due to the exchange of an oxygen donor atom in the crown ether backbone by a nitrogen donor supplied by the redox group, is tightly coupled to the rotation of the dimethylaminophenyl group with respect to the plane of the macrocycle. Gas-phase selectivities favor the more highly charge-dense cations, while the explicit addition of only a few waters of hydration in the calculations recovers the selectivities expected in solution. The alkali metal binding affinity to the singly oxidized Wurster's crown is significantly diminished, while it is completely eliminated for the doubly oxidized ligand.

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). The ability of these ligands to form complexes with platinum(II) was investigated by various techniques including 1H NMR spectroscopy, electrospray mass spectrometry, cyclic voltammetry, and single-crystal X-ray analysis. The traditional crown geometry proved to be better at forming stable endocyclic complexes with Pt(II) than the crownophane geometry. The square-planar Pt(II) crown complex includes direct bonding to the redox center (Pt1-N1 = 2.125 angstroms and Pt1-S(av) = 2.278 angstroms) with concomitant polarization of the phenylenediamine moiety. This results in the crown complex oxidizing 916 mV more anodically than the free ligand. In contrast, modest shifts in the oxidation potential of the crownophane isomer indicate poor interaction between the redox center and complexed Pt(II) ion.

"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. METHOD: A corneal-reflectance, PC-based system (Eyegaze Development System, LC Technologies) provided eye movement measures. Stimuli were four digits in a rectangular array, changed at an event rate of 4 s for a task duration of 30 min. There were 20 subjects who were asked to respond to specific, infrequent signal arrays by bar press, under both 50 dBA white noise and 90 dBA intermittent and unpredictable sound-burst conditions, counterbalanced for order. RESULTS: With time-on-task, subjective fatigue ratings increased, dwell time defined as the total duration of fixations on target digits decreased, number of fixations decreased, and fixations were further from target digits in both conditions. Fixation durations [mean (M) = 258 ms; standard deviation (SD) = 54 ms] did not change significantly with time or condition. Off-target visual scan-paths were less frequently followed by hits than were on-target scan-paths in both conditions. With the sound-burst condition, fixations were closer to target digits and hit rates increased. CONCLUSIONS: Dwell time, number, and accuracy of fixations on target objects decreased with time on task, and inaccurate scan-paths were often associated with performance errors. Sound bursts increased fixation accuracy and hit rate. The results provide a basis for visual scan analyses during vigilance tasks, with applications to alertness monitoring and prediction.