Direct synthesis of previously inaccessible bridgehead azabicyclics by intramolecular cyclization of alpha-sulfonamido and alpha-sulfonimido radicals

Syntheses of the first bridgehead sultams and the only known bridgehead disulfonimide are described. Both approaches capitalize on the electrophilicity of alpha-sulfonyl radicals and their propensity to undergo intramolecular ring closure. Where double bonds are concerned, 5-exo and 6-exo pathways operate preferentially as long as structural strain is not excessive. When the reaction center is a carbon-carbon triple bond, the first cyclization gives rise to vinyl radicals that hold sufficient reactivity to capture solvent benzene. In the case of 45, this sequential reaction leads importantly to the introduction of a styrene functionality sufficiently activated to allow a second ring closure to be kinetically feasible. The solid-state structural features of 12 and 17 have been elucidated by X-ray crystallographic methods. Despite key differences from the norm in the alignment of the nitrogen lone pair relative to the adjacent sulfonyl groups, these compounds exhibit good hydrolytic stability. For 13, generation of the alpha-sulfonamide carbanion is possible and regiospecific oxidation with chromyl acetate has been achieved.     

A convenient method for removing all highly-colored byproducts generated during olefin metathesis reactions

[formula: see text] Addition of a very modest amount of lead tetraacetate (1.50 equiv relative to the amount of Grubbs catalyst) to ring-closing metathesis reaction mixtures effectively removes all colored ruthenium and phosphine impurities to deliver colories reaction products.     

Ultraviolet-B radiation effects on the structure and function of lower trophic levels of the marine planktonic food web

The impact of UV-B radiation (UVBR; 280-320 nm) on lower levels of a natural plankton assemblage (bacteria, phytoplankton and microzooplankton) from the St. Lawrence Estuary was studied during 9 days using several immersed outdoor mesocosms. Two exposure treatments were used in triplicate mesocosms: natural UVBR (N treatment, considered as the control treatment) and lamp-enhanced UVBR (H treatment, simulating 60% depletion of the ozone layer). A phytoplankton bloom developed after day 3, but no significant differences were found between treatments during the entire experiment for phytoplankton biomass (chlorophyll a and cell carbon) nor for phytoplankton cell abundances from flow cytometry and optical microscopy of three phytoplankton size classes (picoplankton, nanoplankton and microplankton). In contrast, bacterial abundances showed significantly higher values in the H treatment, attributed to a decrease in predation pressure due to a dramatic reduction in ciliate biomass (approximately 70-80%) in the H treatment relative to the N treatment. The most abundant ciliate species were Strombidinium sp., Prorodon ovum and Tintinnopsis sp.; all showed significantly lower abundances under the H treatment. P. ovum was the less-affected species (50% reduction in the H treatment compared with that of the N control), contrasting with approximately 90% for the other ones. Total specific phytoplanktonic and bacterial production were not affected by enhanced UVBR. However, both the ratio of primary to bacterial biomass and production decreased markedly under the H treatment. In contrast, the ratio of phytoplankton to bacterial plus ciliate carbon biomass showed an opposite trend than the previous results, with higher values in the H treatment at the end of the experiment. These results are explained by the changes in the ciliate biomass and suggest that UVBR can alter the structure of the lower levels of the planktonic community by selectively affecting key species. On the other hand, linearity between particulate organic carbon (POC) and estimated planktonic carbon was lost during the postbloom period in both treatments. On the basis of previous studies, our results can be attributed to the aggregation of carbon released by cells to the water column in the form of transparent exopolymer particles (TEPs) under nutrient limiting conditions. Unexpectedly, POC during such a period was higher in the H treatment than in controls. We hypothesize a decrease in the ingestion of TEPs by ciliates, in coincidence with increased DOC release by phytoplankton cells under enhanced UVBR. The consequences of such results for the carbon cycle in the ocean are discussed.     

Operator algebras and a theorem of Dieudonne

LetA be aC*-algebra with second dualA″. Let (φ _n)(n=1,...) be a sequence in the dual ofA such that limφ _n(a) exists for eacha εA. In general, this does not imply that limφ _n(x) exists for eachx εA″. But if limφ _n(p) exists whenever p is the range projection of a positive self-adjoint element of the unit ball ofA, then it is shown that limφ _n(x) does exist for eachx inA″. This is a non-commutative generalisation of a celebrated theorem of Dieudonné. A new proof of Dieudonné’s theorem, for positive measures, is given here. The proof of the main result makes use of Dieudonné’s original theorem.     

Effects of enhanced UV-B on pigment-based phytoplankton biomass and composition of mesocosm-enclosed natural marine communities from three latitudes

A series of three outdoor mesocosm experiments was undertaken in Rimouski (Canada), Ubatuba (Brazil) and Ushuaia (southern Argentina) to examine the effects of lamp-enhanced UV-B (280-320 nm) on phytoplankton communities isolated from seawater at each site. Detailed pigment composition was used to identify these communities. Each experiment compared three replicated UV-B treatments, consisting of natural sunlight conditions (NUVB), low-level UV-B enhancement corresponding to local 30% ozone depletion (LUVB) and high-level enhancement corresponding to 60% ozone depletion (HUVB). Each mesocosm (ca 2 m deep) was mixed continuously (turnover time, ca 1.3 h) and samples were obtained daily over 7-10 days. In Rimouski a large diatom bloom occurred during the first week. Repeated-measures analysis of variance (RM-ANOVA), with time as the repeated factor, showed slight but statistically significant increases in the chlorophyll (Chl) a level with the HUVB treatment, which were especially obvious over the last 3 days of the experiment. A large decrease in grazers (ciliates) that was observed concurrently with this treatment is the most likely explanation for the increase in Chl a level. The lack of negative effect on algal biomass by enhanced UV-B is attributed to the mixing inside the mesocosms and to the relatively low UV-B penetration. In Ubatuba levels of most pigments decreased over time, particularly fucoxanthin, Chl c3 and alloxanthin. The RM-ANOVA showed no effect of the UV-B treatments, except for Chl c3, which had significantly lower concentrations under natural UVB conditions, indicating that enhanced UV-B directly or indirectly favored Chl c3 algae (likely prymnesiophytes). Although particulate organic carbon concentration was significantly larger during HUVB treatment than during the other treatments, Chl a was unaffected, suggesting that enhanced UV-B favored heterotrophs. Lack of algal growth during this experiment was attributed to low nutrient concentrations (which were the lowest of the three sites), high irradiances (which were the highest noon incident photosynthetically available radiation and UV of the three sites) and UV-B penetration down to the bottom of the mesocosms. In Ushuaia a small bloom took place over the first 5 days. The RM-ANOVA showed no overall effect of the UV-B treatments for any of the pigments examined but on the last 3 days of the experiment several green algae-type pigments, such as Chl b and siphonein, showed increased concentrations under the HUVB treatment. UV-B enhancement hence favored green algae, as seen from the stronger increase over time in the ratio of Chl b to Chl a associated with the HUVB treatment. UV-B enhancement also seemed to cause a slight decrease in physiological condition, because the relative concentration of chlorophyllide a and some pheophorbides that may be the product of dying algae increased during the HUVB treatments in Ubatuba and particularly in Ushuaia (where UV-B also penetrated to the bottom of mesocosms). For all three sites changes in phytoplankton biomass due to the UV-B treatments were minor, even though UV-B enhancement was important. This study indicates that effects of enhanced UV-B on the community structure of both phytoplankton and their grazers are potentially more important than effects on overall algal biomass.     

Metal-specific interactions of H2 adsorbed within isostructural metal-organic frameworks

Diffuse reflectance infrared (IR) spectroscopy performed over a wide temperature range (35-298 K) is used to study the dynamics of H(2) adsorbed within the isostructural metal-organic frameworks M(2)L (M = Mg, Mn, Co, Ni and Zn; L = 2,5-dioxidobenzene-1,4-dicarboxylate) referred to as MOF-74 and CPO-27. Spectra collected at H(2) concentrations ranging from 0.1 to 3.0 H(2) per metal cation reveal that strongly red-shifted vibrational modes arise from isolated H(2) bound to the available metal coordination site. The red shift of the bands associated with this site correlate with reported isosteric enthalpies of adsorption (at small surface coverage), which in turn depend on the identity of M. In contrast, the bands assigned to H(2) adsorbed at positions >3 ? from the metal site exhibit only minor differences among the five materials. Our results are consistent with previous models based on neutron diffraction data and independent IR studies, but they do not support a recently proposed adsorption mechanism that invokes strong H(2)···H(2) interactions (Nijem et al. J. Am. Chem. Soc.2010, 132, 14834-14848). Room temperature IR spectra comparable to those on which the recently proposed adsorption mechanism was based were only reproduced after contaminating the adsorbent with ambient air. Our interpretation that the uncontaminated spectral features result from stepwise adsorption at discrete framework sites is reinforced by systematic red shifts of adsorbed H(2) isotopologues and consistencies among overtone bands that are well-described by the Buckingham model of molecular interactions in vibrational spectroscopy.