Facile in situ copper(ii) mediated C–S bond activation transforming dithiocarbimate to carbamate and thiocarbamate generating Cu(ii) and Cu(i) complexes

Facile in situ Cu(II) mediated transformation of p-tolylsulfonyldithiocarbimate in conjunction with polypyridyl or phosphine ligands into corresponding carbamate and thiocarbamate led to the formation of new copper complexes with varying nuclearities and geometries, via C-S bond activation of the ligand within identical reaction systems.

Effect of an ancillary ligand on single helix-double helix interconversion in copper complexes. Copper(I)-water bond

Reaction of Cu(ClO(4))(2)center dot 6H(2)O with the 1:2 condensate of benzildihydrazone and 2-acetylpyridine, in methanol in equimolar ratio yields a green compound which upon recrystallisation from 1:1 CH(2)Cl(2)-C(6)H(6) mixture affords [CuL(H(2)O)](ClO(4))(2)center dot 1/2C(6)H(6). The complex crystallises in the space group P-1 with a = 8.028(11) angstrom, b = 12.316(17) angstrom, c = 18.14(3) angstrom, alpha = 97.191(10)degrees, beta = 94.657(10)degrees and gamma = 108.039(10)degrees. It is single helical with the metal having a distorted trigonal bipyramidal N(4)O coordination sphere. The acid dissociation constant of the Cu(I) complex in CH(3)CN is 3.34 +/- 0.19. The X band EPR spectrum of the compound is rhombic with g(1) = 2.43, g(2) = 2.10 g(3) = 2.02 and A(1) = 79.3 x 10(-4) cm(-1). The Cu(II/I) potential of the complex in CH(2)Cl(2) at a glassy carbon electrode is 0.43 V vs SCE. It is argued that the copper-water bond persists in the corresponding copper(I) species. Its implications on the single helix-double helix interconversion in copper helicates are discussed. DFT calculations at the B3LYP/6-311G** level shows that the binding energy of water in the single helicol live-coordinate copper(I) species [CuL(H(2)O)](+) is similar to 40 kJ mol(-1).

Homoleptic copper(II) and copper(I) complexes of 5,6-dihydro-5,6-epoxy-1,10-phenanthroline. Six-coordinate copper(I) in solution

Reaction of 5,6-dihydro-5,6-epoxy-1,10-phenanthroline (L) with Cu(ClO(4))(2)center dot 6H(2)O in methanol in 3:1 M ratio at room temperature yields light green [CuL(3)](ClO(4))(2)center dot H(2)O (1). The X-ray crystal structure of the hemi acetonitrile solvate [CuL(3)](ClO(4))(2)center dot 0.5CH(3)CN has been determined which shows Jahn-Teller distortion in the CuN(6) core present in the cation [CuL(3)](2+). Complex 1 gives an axial EPR spectrum in acetonitrile-toluene glass with g(parallel to) = 2.262 (A(parallel to) = 169 x 10 (4) cm (1)) and g(perpendicular to) = 2.069. The Cu(II/I) potential in 1 in CH(2)Cl(2) at a glassy carbon electrode is 0.32 V versus NHE. This potential does not change with the addition of extra L in the medium implicating generation of a six-coordinate copper(I) species [CuL(3)](+) in solution. B3LYP/LanL2DZ calculations show that the six Cu-N bond distances in [CuL(3)](+) are 2.33, 2.25, 2.32, 2.25, 2.28 and 2.25 angstrom while the ideal Cu(I)-N bond length in a symmetric Cu(I)N(6) moiety is estimated as 2.25 angstrom. Reaction of L with Cu(CH(3)CN)(4)ClO(4) in dehydrated methanol at room temperature even in 4:1 M proportion yields [CuL(2)]ClO(4) (2). Its (1)H NMR spectrum indicates that the metal in [CuL(2)](+) is tetrahedral. The Cu(II/I) potential in 2 is found to be 0.68 V versus NHE in CH(2)Cl(2) at a glassy carbon electrode. In presence of excess L, 2 yields the cyclic voltammogram of 1. From (1)H NMR titration, the free energy of binding of L to [CuL(2)](+) to produce [CuL(3)](+) in CD(2)Cl(2) at 298 K is estimated as -11.7 (+/-0.2) kJ mol (1).

I owe you: age-related similarities and differences in associative memory for gains and losses

Older adults often experience associative memory impairments but can sometimes remember important information. The current experiments investigate potential age-related similarities and differences associate memory for gains and losses. Younger and older participants were presented with faces and associated dollar amounts, which indicated how much money the person “owed” the participant, and were later given a cued recall test for the dollar amount. Experiment 1 examined face-dollar amount pairs while Experiment 2 included negative dollar amounts to examine both gains and losses. While younger adults recalled more information relative to older adults, both groups were more accurate in recalling the correct value associated with high value faces compared to lower value faces and remembered gist-information about the values. However, negative values (losses) did not have a strong impact on recall among older adults versus younger adults, illustrating important associative memory differences between younger and older adults.

I killed my father, I ate human flesh, I quiver with joy: an obsession with Pier Paolo Pasolini

Group show, curated by Invisible Exports Gallery. Featuring work by Michael Bilsborough, Lizzi Bougatsos, BREYER P-ORRIDGE, Asger Carlsen, Troels Carlsen, Walt Cassidy, Andy Coolquitt, Vaginal Davis, Carlton DeWoody, Joey Frank, Paul Gabrielli, Ludovica Gioscia, Luis Gispert, Terence Hannum, Karen Heagle, Timothy Hull, Doug Ischar, Brian Kenny, Jeremy Kost, Aaron Krach, Yeni Mao, Leigha Mason, Mark McCoy, Robert Melee, Lucas Michael, Jennifer Needleman, Brent Owens, Paul P., Paolo Di Paolo, Franklin Preston, John Russell, Xaviera Simmons, Duston Spear, Scott Treleaven, Ramon Vega, Jordan Wolfson, Dustin Yellin

You know how I know you're gay? : masculinity and homophobia in mainstream comedy

You Know How I Know You're Gay?: Masculinity and Homophobia in Contemporary Mainstream Comedy is a three-part senior scholars project that consists of a critical analysis of homophobic humor in contemporary mainstream comedy, an original feature-length comedy script entitled Don 't Be that Freshman, and a DVD of selected scenes from Don't Be that Freshman. The critical analysis first establishes the existence of homophobic humor in mainstream comedy and then links this homophobia to masculine anxiety, applying the ideas set forth in Michael Kimmel's essay, "Masculinity as Homophobia," to contemporary, mainstream, homosocial comedies. The paper goes on to examine audience reactions to this homophobic humor, focusing on audience members who enjoy these movies, yet consider themselves to be accepting of homosexuality and against homophobia. I discuss ways of resistance and the importance of opposing homophobic humor, and finally, I look at comedy as a potentially transgressive medium that could be used to fight homophobia and social inequality. The critical analysis, therefore, leads into Don't Be that Freshman, a film that uses progressive humor to oppose homophobia and expose the potential dangers and pitfalls of conforming to social constructions of gender. Don't Be that Freshman is a film about three pairs of college roommates in their first semester at college who become each other's first friends on campus. It is a character-driven comedy that attempts to normalize non-heterosexual sexual orientation and gender non-conformity, to advocate a type of living that does not conform to problematic social constructions and cultural ideologies, and at the same time to appeal to a mainstream audience. The film version is twenty-five minutes long and consists of ten scenes from the script.

Long-Term Adult Population Fluctuations and Distribution of the Spot, <i>Leiostomus xanthurusi>, in Mississippi

Adult specimens of the spot. Leiostomus xanthurus, were collected from bayou, Mississippi Sound, and barrier island locations along the Gulf Coast of Mississippi from November 1982 to July 1989. 7he mean total length of all spot sampled in comparable gill net sets was 219 mm (± 14 standard deviation, n=4,338). Ninety-five percent of the spot were collected in the island and sound areas, where the salinity was higher than in the bayous. Catch per unit effort was high at island and sound stations in spring and autumn, with relatively few fish caught during the winter spawning season and summer. The relatively high frequency of spot observed at the island stations in the autumn was probably influenced by spawning migrations, and the high spring values may represent a combination of two abundant year classes. The two greatest yearly collections, in 1983 and 1986, may have been influenced by sampling conditions or by environmental conditions favorable to survival either during those years or earlier when those fish were postlarvae. The smallest yearly catch occurred in 1985 and may have reflected the harsh weather conditions that year.

Evaluation of operational SSM/I ice-concentration algorithms

The United States National Ice Center (NIC) provides weekly ice analyses of the Arctic and Antarctic using information from ice reconnaissance, ship reports and high-resolution satellite imagery. In cloud-covered areas and regions lacking imagery, the higher-resolution sources are augmented by ice concentrations derived from Defense Meteorological Satellite Program (DMSP) Special Sensor Microwave/Imager (SSMII) passive-microwave imagery. However, the SSMII-derived ice concentrations are limited by low resolution and uncertainties in thin-ice regions. Ongoing research at NIC is attempting to improve the utility of these SSMII products for operational sea-ice analyses. The refinements of operational algorithms may also aid future scientific studies. Here we discuss an evaluation of the standard operational ice-concentration algorithm, Cal/Val, with a possible alternative, a modified NASA Team algorithm. The modified algorithm compares favorably with CallVal and is a substantial improvement over the standard NASA Team algorithm in thin-ice regions that are of particular interest to operational activities.

Geographic Variation in Sea Otters, <i>Enhydra lutrisi>

Univariate and multivariate analyses of 20 skull characters of 304 adult sea otters from throughout the geographic range strongly suggest that three subspecies should be recognized. The nominate form, Enhydra lutris lutris, occurs from the Kuril Islands north to the Commander Islands in the western Pacific Ocean. Individuals of E. l. lutris are characterized by large size and wide skulls with short nasal bones. E. 1. nereis is found along the California coast and off San Nicolas Island, where the species recently has been reintroduced from coastal California. Specimens of E. 1. nereis have narrow skulls with a long rostrum and small teeth, and usually lack the characteristic notch in the postorbital region found in most specimens of the other two subspecies. A new subspecies described by Don E. Wilson in this report, occurs throughout the Aleutian Islands and southward in the eastern Pacific to Washington. Specimens of the new subspecies are intermediate in size in most, but not all, characters and have longer mandibles than either of the other two subspecies

Book Review of <i> Twilight of the Mammoths: Ice Age Extinctions and the Rewilding of Americai> by Paul S. Martin

Applying ecological studies to the adaptations of prehistoric human hunter-gatherer groups has greatly increased our abilities to interpret effects of an ever-changing environment and our access to critical resources on these populations. The Pleistocene/Holocene transition, its climate and human genesis in the new world, draws intensive interest from a number of scientific communities. In Twilight of the Mammoths, Paul Martin adds his views, which are of no surprise, on the megafaunal extirpations during a cultural period referred to in North America as Clovis.

Hunting and social behaviour of leopard seals (<i>Hydrurga leptonyxi>) at Seal Island, South Shetland Islands, Antarctica

The hunting behavior of leopard seals Hydrurga leptonyx was monitored opportunistically at Seal Island, South Shetland Islands, during the austral summers from 1986/87 to 1994/95. Leopard seals used several methods to catch Antarctic fur seal pups Arctocephalus gazella and chinstrap penguins Pygoscelis antarctica, and individuals showed different hunting styles and hunting success. One to two leopard seals per year were responsible for an average of 60% of observed captures of fur seal pups. Leopard seals preyed on penguins throughout the summer, but preyed on fur seal pups only between late December and mid-February. Hunting behavior differed significantly between different locations on the island; fur seals were hunted only at one colony, and penguins were hunted in several areas. The relative abundance of prey types, size of prey in relation to predator, and specialization of individual leopard seals to hunt fur seal prey probably influence individual prey preferences among leopard seals. On five occasions, two leopard seals were seen together on Seal Island. Possible interpretations of the relationship between the interacting leopard seals included a mother-offspring relationship, a consorting male-female pair, and an adult leopard seal followed by an unrelated juvenile. In two incidents at Seal Island, two leopard seals were observed interacting while hunting: one seal captured fur seal pups and appeared to release them to the other seal. Observations of leopard seals interacting during hunting sessions were difficult to confirm as co-operative hunting, but they strongly implied that the two seals were not agonistic toward one another. The hunting success of individual leopard seals pursuing penguins or fur seals is probably high enough for co-operative hunting not to become a common hunting strategy; however, it may occur infrequently when it increases the hunting productivity of the seals.

Mandibular fractures in short-finned pilot whales, <i>Globicephala macrorhynchusi>

This study’s objective was to investigate mandibular fractures in 50 short-finned pilot whales, Globicephala macrorhynchus, from two mass strandings. Based on current theories that this species is sexually dimorphic and polygynous, hypotheses were: (1) males should suffer more frequent or more substantial mandibular fractures than should females, and (2) fracture occurrence should increase with male reproductive maturity and potential correlates of maturity, such as age and length. Fractures were described and correlated with physical characteristics to infer possible explanations for injuries. Mandibular fractures were surprisingly common in males and females, being found in more than half of the animals examined (27/50, or 54% overall; 17/36 or 47% of females and 10/14 or 71% of males). Length was the only correlate of fracture presence; the proportion of animals showing evidence of fracture increased with length. These results offer some support to initial hypotheses, but there must be another set of consequences that contribute to mandibular fractures in females. A combination of intra- and interspecific interactions and life history characteristics may be responsible for fractures. Further research from a larger sample of this and other cetacean species are suggested to help elucidate both the causes and implications of mandibular fractures.