Persistent organic pollutants in the Atlantic and southern oceans and oceanic atmosphere

Persistent organic pollutants (POPs) continue to cycle through the atmosphere and hydrosphere despite banned or severely restricted usages. Global scale analyses of POPs are challenging, but knowledge of the current distribution of these compounds is needed to understand the movement and long-term consequences of their global use. In the current study, air and seawater samples were collected Oct. 2007–Jan. 2008 aboard the Icebreaker Oden en route from Göteborg, Sweden to McMurdo Station, Antarctica. Both air and surface seawater samples consistently contained α-hexachlorocyclohexane (α-HCH), γ-HCH, hexachlorobenzene (HCB), α-Endosulfan, and polychlorinated biphenyls (PCBs). Sample concentrations for most POPs in air were higher in the northern hemisphere with the exception of HCB, which had high gas phase concentrations in the northern and southern latitudes and low concentrations near the equator. South Atlantic and Southern Ocean seawater had a high ratio of α-HCH to γ-HCH, indicating persisting levels from technical grade sources. The Atlantic and Southern Ocean continue to be net sinks for atmospheric α-, γ-HCH, and Endosulfan despite declining usage

A new monotypic family for the enigmatic crustose red alga Plagiospora gracilis.

Plagiospora gracilis, a mucilaginous crustose red alga growing on subtidal pebbles on both coasts of the North Atlantic Ocean, forms distinctive tetrasporangia (red algal meiotic structures that release haploid tetraspores) but gametophytes have never been reported. In the absence of gametangia, the taxonomic position of this monotypic genus has always been uncertain; it is currently placed provisionally in the Gloiosiphoniaceae (Gigartinales) by comparison with sporophytes of Gloiosiphonia obtained in culture. Dioecious gametophytic crusts of P. gracilis are now reported for the first time, forming gametangia in inconspicuous superficial sori. There is no evidence that fertilization ever occurs in the field although fertile males and female were collected together. In culture, tetraspores grew into tetrasporophytes for three successive generations, by presumed apomictic sporophyte recycling. The life history of P. gracilis may represent a late stage in the loss of sexual reproduction leading to tetraspore-to-tetrasporophyte life histories such as that in Hildenbrandia. Phylogenetic analysis of sequences of the rbcL, LSU (28S) rDNA and coxI (COI-5P) genes for P. gracilis with other Gigartinales resolved P. gracilis as a distinct lineage in a well-supported clade of the families Sphaerococcaceae, Gloiosiphoniaceae, Endocladiaceae, Nizymeniaceae and Phacelocarpaceae. We here propose the monotypic Plagiosporaceae fam. nov. to accommodate P. gracilis

Multigene analyses resolve early diverging lineages in the Rhodymeniophycidae (Florideophyceae, Rhodophyta).

Multigene phylogenetic analyses were directed at resolving the earliest divergences in the red algal subclass Rhodymeniophycidae. The inclusion of key taxa (new to science and/or previously lacking molecular data), additional sequence data (SSU, LSU, EF2, rbcL, COI-5P), and phylogenetic analyses removing the most variable sites (site stripping) have provided resolution for the first time at these deep nodes. The earliest diverging lineage within the subclass was the enigmatic Catenellopsis oligarthra from New Zealand (Catenellopsidaceae), which is here placed in the Catenellopsidales ord. nov. In our analyses Atractophora hypnoides was not allied with the other included Bonnemaisoniales, but resolved as sister to the Peyssonneliales, and is here assigned to Atractophoraceae fam. nov. in the Atractophorales ord. nov. Inclusion of Acrothesaurum gemellifilum gen. et sp. nov. from Tasmania has greatly improved our understanding of the Acrosymphytales, to which we assign three families, the Acrosymphytaceae, Acrothesauraceae fam. nov. and Schimmelmanniaceae fam. nov. This article is protected by copyright. All rights reserved

Synthesis, Characterization, And Catalytic And Biological Activities of A Mixed-ligand Cobalt(ii) Bipyridyl/diphenylazodioxide Complex

Transition metal complexes have immense importance in the pharmaceutical industry. These types of complexes can be useful catalysts in the synthesis of medicinal compounds and can act as anticancer drugs. In these pharmaceutical applications, 1st-row transition metal-containing complexes offer certain advantages compared to their 2nd and 3rd-row transition metal counterparts. Our motivation was to investigate pharmaceutical applications of transition metal complexes containing both a 1st-row transition metal and unusual ligands to expand the knowledge of a class of complexes that could potentially be beneficial in the pharmaceutical industry. A class of rare ligands that piqued our interest was that of the diaryl azodioxides, cis-Ar(O)NN(O)Ar, which belong to the wider class of organic derivatives of nitric oxide (NO). Our synthesis and pharmaceutical applications of the azodioxide complex salt [Co(bpy){Ph(O)NN(O)Ph}2](PF6)2 have been able to significantly expand the knowledge of azodioxide complexes by displaying an unusual trigonal prismatic coordination geometry for cobalt(II) with only bidentate ligands, showing evidence of ligand-based redox activity, acting as an active catalyst in allylic amination/C-C double-bond transposition reactions, and selectively inducing apoptosis in SK-HEP-1 human liver adenocarcinoma cells. Importantly, catalytic and biological studies of [Co(bpy){Ph(O)NN(O)Ph}2](PF6)2 are ongoing, and focused on its potential for use in the pharmaceutical industry as a drug or catalyst for drug synthesis. Future work will vi involve comparing the catalytic and biological activities of [Co(bpy){Ph(O)NN(O)Ph}2](PF6)2 with other azodioxide complexes prepared by our group to identify structure-activity relationships and inform the design of more efficient catalysts and anti-cancer, pro-apoptotic agents

Analysis of chloroplast genomes and a supermatrix inform reclassification of the Rhodomelaceae (Rhodophyta).

With over a thousand species, the Rhodomelaceae is the most species-rich family of red algae. While its genera have been assigned to 14 tribes, the high-level classification of the family has never been evaluated with a molecular phylogeny. Here, we reassess its classification by integrating genome-scale phylogenetic analysis with observations of the morphological characters of clades. In order to resolve relationships among the main lineages of the family we constructed a phylogeny with 55 chloroplast genomes (52 newly determined). The majority of branches were resolved with full bootstrap support. We then added 266 rbcL, 125 18S rRNA gene and 143 cox1 sequences to construct a comprehensive phylogeny containing nearly half of all known species in the family (407 species in 89 genera). These analyses suggest the same subdivision into higher-level lineages, but included many branches with moderate or poor support. The circumscription for nine of the 13 previously described tribes was supported, but the Lophothalieae, Polysiphonieae, Pterosiphonieae and Herposiphonieae required revision, and five new tribes and one resurrected tribe were segregated from them. Rhizoid anatomy is highlighted as a key diagnostic character for the morphological delineation of several lineages. This work provides the most extensive phylogenetic analysis of the Rhodomelaceae to date and successfully resolves the relationships among major clades of the family. Our data show that organellar genomes obtained through high-throughput sequencing produce well-resolved phylogenies of difficult groups, and their more general application in algal systematics will likely permit deciphering questions about classification at many taxonomic levels

Analysis of chloroplast genomes and a supermatrix inform reclassification of the Rhodomelaceae (Rhodophyta).

With over a thousand species, the Rhodomelaceae is the most species-rich family of red algae. While its genera have been assigned to 14 tribes, the high-level classification of the family has never been evaluated with a molecular phylogeny. Here, we reassess its classification by integrating genome-scale phylogenetic analysis with observations of the morphological characters of clades. In order to resolve relationships among the main lineages of the family we constructed a phylogeny with 55 chloroplast genomes (52 newly determined). The majority of branches were resolved with full bootstrap support. We then added 266 rbcL, 125 18S rRNA gene and 143 cox1 sequences to construct a comprehensive phylogeny containing nearly half of all known species in the family (407 species in 89 genera). These analyses suggest the same subdivision into higher-level lineages, but included many branches with moderate or poor support. The circumscription for nine of the 13 previously described tribes was supported, but the Lophothalieae, Polysiphonieae, Pterosiphonieae and Herposiphonieae required revision, and five new tribes and one resurrected tribe were segregated from them. Rhizoid anatomy is highlighted as a key diagnostic character for the morphological delineation of several lineages. This work provides the most extensive phylogenetic analysis of the Rhodomelaceae to date and successfully resolves the relationships among major clades of the family. Our data show that organellar genomes obtained through high-throughput sequencing produce well-resolved phylogenies of difficult groups, and their more general application in algal systematics will likely permit deciphering questions about classification at many taxonomic levels

The genera Melanothamnus Bornet & Falkenberg and Vertebrata S.F. Gray constitute well-defined clades of the red algal tribe Polysiphonieae (Rhodomelaceae, Ceramiales).

Polysiphonia is the largest genus of red algae, and several schemes subdividing it into smaller taxa have been proposed since its original description. Most of these proposals were not generally accepted, and currently the tribe Polysiphonieae consists of the large genus Polysiphonia (190 species), the segregate genus Neosiphonia (43 species), and 13 smaller genera (< 10 species each). In this paper, phylogenetic relationships of the tribe Polysiphonieae are analysed, with particular emphasis on the genera Carradoriella, Fernandosiphonia, Melanothamnus, Neosiphonia, Polysiphonia sensu stricto, Streblocladia and Vertebrata. We evaluated the consistency of 14 selected morphological characters in the identified clades. Based on molecular phylogenetic (rbcL and 18S genes) and morphological evidence, two speciose genera are recognized: Vertebrata (including the type species of the genera Ctenosiphonia, Enelittosiphonia, Boergeseniella and Brongniartella) and Melanothamnus (including the type species of the genera Fernandosiphonia and Neosiphonia). Both genera are distinguished from other members of the Polysiphonieae by synapomorphic characters, the emergence of which could have provided evolutionarily selective advantages for these two lineages. In Vertebrata trichoblast cells are multinucleate, possibly associated with the development of extraordinarily long, photoprotective, trichoblasts. Melanothamnus has 3-celled carpogonial branches and plastids lying exclusively on radial walls of the pericentral cells, which similarly may improve resistance to damage caused by excessive light. Other relevant characters that are constant in each genus are also shared with other clades. The evolutionary origin of the genera Melanothamnus and Vertebrata is estimated as 75.7-95.78 and 90.7-138.66 Ma, respectively. Despite arising in the Cretaceous, before the closure of the Tethys Seaway, Melanothamnus is a predominantly Indo-Pacific genus and its near-absence from the northeastern Atlantic is enigmatic. The nomenclatural implications of this work are that 46 species are here transferred to Melanothamnus, six species are transferred to Vertebrata and 13 names are resurrected for Vertebrata

Implementation and effects of user participation in playground management: a comparative study of two Swedish municipalities

This paper describes and analyses how customer orientation strategies, with the focus on user participation, are implemented in playground management and their effects on managers’ attitudes and work with physical playgrounds. A comparative case study was conducted in two Swedish municipalities that involve users in different ways: through a manager-driven participation process and through informal user-initiated dialogue. The empirical material consisted of qualitative interviews with professionals in the management organisations and studies of local playgrounds. Implementation of strategies for user participation and tactical management activities appeared to be of importance. The manager-driven participation strategy was associated with a particularly positive attitude among managers, but also difficulties such as maintaining continuous dialogue with users. The small differences found in playground provision between the two municipalities give reason to question the physical effects of participation processes, and show the need for further research

Allylic Amination and Carbon–carbon Double Bond Transposition Catalyzed by Cobalt(II) azodioxide Complexes

The unusual cobalt(II) diphenylazodioxide complex salts [Co(az)4](PF6)2 and [Co(bpy)(az)2](PF6)2 have been shown to catalyze the allylic amination/C–C double bond transposition reaction of 2-methyl-2-pentene with PhNHOH, with a turnover number of about 4. The mechanism is proposed to involve a nitroso-ene-like transfer of a PhNO moiety from the azodioxide ligand to the alkene, followed by reduction of the organic product to yield a cobalt(III) intermediate, which is itself reduced back to cobalt(II) by PhNHOH, regenerating PhNO. Hetero-Diels-Alder trapping experiments suggest that an “off-metal” mechanism, in which PhNO is released from the cobalt complexes and reacts with the alkenes, is operative, in contrast to an “on-metal” mechanism observed by Nicholas and coworkers for [Fe(az)3](FeCl4)2