Absolute Configuration and Biosynthesis of Pahayokolide A from Lyngbya sp. Strain 15-2 of the Florida Everglades

Pahayokolides A-D are cytotoxic cyclic polypeptides produced by the freshwater cyanobacterium Lyngbya sp. strain 15-2 that possess an unusual β-amino acid, 3-amino-2,5,7,8-tetrahydroxy-10-methylundecanoic acid (Athmu). The absolute configuration of pahayokolides A-D was determined using advanced Marfey’s method. It was also confirmed that a pendant N-acetyl-N-methyl leucine moiety in pahayokolide A was absent in pahayokolides B and pahayokolides C-D were conformers of pahayokolide A. Feeding experiments indicated that the biosynthesis of the Athmu sidechain arises from leucine or α-ketoisovalerate, however could not be further extended by three rounds of condensation with malonate units. Putative four peptide and one unique polyketide synthetases in Lyngbya sp. strain 15-2 were identified by using a PCR method and degenerate primers derived from conserved core sequences of known NRPSs and PKSs. Identification of one unique KS domain conflicted with the logic rule that the long side chain of Athmu was assembled by three rounds of ketide extensions if PKSs were involved. A gene cluster (pah) encoding a peptide synthetase putatively producing pahayokolide was cloned, partially sequenced and characterized. Seven modules of the non-ribosomal peptide synthetase (NRPS) were identified. Ten additional opening reading frames (ORFs) were found, responsible for peptide resistance, transport and degradation. Although the predicted substrate specificities of NRPS agreed with the structure of pahayokolide A partially, the disagreement could be explained. However, no PKS gene was found in the pah gene cluster.

(Table 1) Physical oceanography during Lance cruise LA99/2 in the marginal ice zone of the Barents Sea

Zooplankton was studied on eight stations in the marginal ice zone (MIZ) of the Barents Sea, in May 1999, along two transects across the ice edge. On each station, physical background measurements and zooplankton samples were taken every 6 h over a 24 h period at five discrete depth intervals. Cluster analysis revealed separation of open water stations from all ice stations as well as high similarity level among replicates belonging to particular station. Based on five replicates per station, analysis of variance (ANOVA) confirmed significant differences (P < 0.05) in abundances of the main mesozooplankton taxa among stations. Relations between the zooplankton community and environmental parameters were established using redundancy analysis (CANOCO). In total, 55% of mesozooplankton variability within studied area was explained by eight variables with significant conditional effects: depth stratum, fluorescence, temperature, salinity, bottom depth, latitude, bloom situation, and ice concentration. GLM models supported supposition about clear and negative relationship between concentration of Oithona similis, and overall mesozooplankton diversity The analyses showed a dynamic relationship between mesozooplankton distribution and hydrological conditions on short-term scale. Furthermore, our study demonstrated that variability in the physical environment of dynamic MIZ of the Barents Sea has measurable effect on the Arctic pelagic ecosystem.

The relation between cool cluster cores and Herschel-detected star formation in brightest cluster galaxies

We present far-infrared (FIR) analysis of 68 brightest cluster galaxies (BCGs) at 0.08 < z < 1.0. Deriving total infrared luminosities directly from Spitzer and Herschel photometry spanning the peak of the dust component (24-500 μm), we calculate the obscured star formation rate (SFR). 22^+6.2 _–5.3% of the BCGs are detected in the far-infrared, with SFR = 1-150 M ☉ yr^–1. The infrared luminosity is highly correlated with cluster X-ray gas cooling times for cool-core clusters (gas cooling time <1 Gyr), strongly suggesting that the star formation in these BCGs is influenced by the cluster-scale cooling process. The occurrence of the molecular gas tracing Hα emission is also correlated with obscured star formation. For all but the most luminous BCGs (L_TIR > 2 × 10^11 L_☉), only a small (≤0.4 mag) reddening correction is required for SFR(Hα) to agree with SFR_FIR. The relatively low Hα extinction (dust obscuration), compared to values reported for the general star-forming population, lends further weight to an alternate (external) origin for the cold gas. Finally, we use a stacking analysis of non-cool-core clusters to show that the majority of the fuel for star formation in the FIR-bright BCGs is unlikely to originate from normal stellar mass loss.

A bright z=5.2 lensed submillimeter galaxy in the field of Abell 773 HLSJ091828.6+514223

During our Herschel Lensing Survey (HLS) of massive galaxy clusters, we have discovered an exceptionally bright source behind the z = 0.22 cluster Abell 773, which appears to be a strongly lensed submillimeter galaxy (SMG) at z = 5.2429. This source is unusual compared to most other lensed sources discovered by Herschel so far, because of its higher submm flux (∼200 mJy at 500 μm) and its high redshift. The dominant lens is a foreground z = 0.63 galaxy, not the cluster itself. The source has a far-infrared (FIR) luminosity of L_FIR = 1.1 × 10^14/μ L_⨀, where μ is the magnification factor, likely ∼11. We report here the redshift identification through CO lines with the IRAM-30 m, and the analysis of the gas excitation, based on CO(7–6), CO(6–5), CO(5–4) detected at IRAM and the CO(2–1) at the EVLA. All lines decompose into a wide and strong red component, and a narrower and weaker blue component, 540 km s^−1 apart. Assuming the ultraluminous galaxy (ULIRG) CO-to-H_2 conversion ratio, the H_2 mass is 5.8×10^11/μ M_⨀, of which one third is in a cool component. From the CI(^3P_2−^3 P_1) line we derive a C_I/H_2 number abundance of 6 × 10^−5 similar to that in other ULIRGs. The H_2O_p(2, 0, 2−1, 1, 1) line is strong only in the red velocity component, with an intensity ratio I(H_2O)/I(CO) ∼ 0.5, suggesting a strong local FIR radiation field, possibly from an active nucleus (AGN) component. We detect the [NII]205 μm line for the first time at high-z. It shows comparable blue and red components, with a strikingly broad blue one, suggesting strong ionized gas flows.

Coordination networks of Cu2+ ions with 1,3-bis[2-(4-pyridyl)ethyl]benzene : strong structure-directing role of the counter ion (nitrate, acetate and sulphate), leading to clusters, sheets and chains

Date of Acceptance: 16/10/2015

Coordination networks of Cu2+ ions with 1,3-bis[2-(4-pyridyl)ethyl]benzene : strong structure-directing role of the counter ion (nitrate, acetate and sulphate), leading to clusters, sheets and chains

Date of Acceptance: 16/10/2015

Photocatalytic activities of tin(IV) oxide surface-modified titanium(IV) dioxide show a strong sensitivity to the TiO 2 crystal form

Surface modification of rutile TiO2 with extremely small SnO2 clusters gives rise to a great increase in its UV light activity for degradation of model organic water pollutants, while the effect is much smaller for anatase TiO2. This crystal form sensitivity is rationalized in terms of the difference in the electronic modification of TiO2 through the interfacial Sn−O−Ti bonds. The increase in the density of states near the conduction band minimum of rutile by hybridization with the SnO2 cluster levels intensifies the light absorption, but this is not seen with modified anatase. The electronic transition from the valence band to the conduction band causes the bulk-to-surface interfacial electron transfer to enhance charge separation. Further, electrons relaxed to the conduction minimum are smoothly transferred to O2 due to the action of the SnO2 species as an electron transfer promoter.

Loading effect in copper(II) oxide cluster-surface-modified titanium(IV) oxide on visible- and UV-light activities

Cu(acac)2 is chemisorbed on TiO2 particles [P-25 (anatase/rutile = 4/1 w/w), Degussa] via coordination by surface Ti–OH groups without elimination of the acac ligand. Post-heating of the Cu(acac)2-adsorbed TiO2 at 773 K yields molecular scale copper(II) oxide clusters on the surface (CuO/TiO2). The copper loading amount (Γ/Cu ions nm–2) is controlled in a wide range by the Cu(acac)2 concentration and the chemisorption–calcination cycle number. Valence band (VB) X-ray photoelectron and photoluminescence spectroscopy indicated that the VB maximum of TiO2 rises up with increasing Γ, while vacant midgap levels are generated. The surface modification gives rise to visible-light activity and concomitant significant increase in UV-light activity for the degradation of 2-naphthol and p-cresol. Prolonging irradiation time leads to the decomposition to CO2, which increases in proportion to irradiation time. The photocatalytic activity strongly depends on the loading, Γ, with an optimum value of Γ for the photocatalytic activity. Electrochemical measurements suggest that the surface CuO clusters promote the reduction of adsorbed O2. First principles density functional theory simulations clearly show that, at Γ < 1, unoccupied Cu 3d levels are generated in the midgap region, and at Γ > 1, the VB maximum rises and the unoccupied Cu 3d levels move to the conduction band minimum of TiO2. These results suggest that visible-light excitation of CuO/TiO2 causes the bulk-to-surface interfacial electron transfer at low coverage and the surface-to-bulk interfacial electron transfer at high coverage. We conclude that the surface CuO clusters enhance the separation of photogenerated charge carriers by the interfacial electron transfer and the subsequent reduction of adsorbed O2 to achieve the compatibility of high levels of visible and UV-light activities.

Identidade regional no cluster comercial da rua Oscar Freire

O objetivo desta pesquisa é verificar manifestações de identidade regional no aglomerado comercial da Rua Oscar Freire. Para os fins propostos, definem-se como componentes da identidade regional sua caracterização empírica, sua imagem e as percepções dos atores em relação à sua existência, bem como sua identificação com o cluster e a disposição para atuar em prol de seu desenvolvimento. A pesquisa é de caráter exploratório e os dados foram obtidos mediante análise de documentos, entrevistas com atores regionais e observação espontânea. As dimensões mais características da imagem da região são: cluster de negócios, rua de luxo, local atraente para empresas, local em que os clientes são bem tratados e modelo para replicação. Verifica-se a existência de identidade regional nesse aglomerado, embora esta seja mais evidente quando se consideram as dimensões cognitiva e afetiva, pois os atores reconhecem a existência do conglomerado comercial, têm consciência de seus limites e de suas funções, e manifestam solidariedade no desempenho das atividades comerciais. A dimensão conativa, que se refere ao desenvolvimento de ações efetivas em prol do desenvolvimento da região, mostra-se menos evidente. Conclui-se que o território, constituído pela Rua Oscar Freire e adjacências, também pode ser considerado uma região socialmente construída, pois além de apresentar abrangência territorial bem definida e uma imagem conceitual e simbólica, faz parte de um sistema de regiões e apresenta identidade regional.

Vocational Rehabilitation in Early Psychosis: Cluster Randomised Trial

Background Individual placement and support (IPS) is effective in helping patients return to work but is poorly implemented because of clinical ambivalence and fears of relapse. Aims To assess whether a motivational intervention (motivational interviewing) directed at clinical staff to address ambivalence about employment improved patients’ occupational outcomes. Method Two of four early intervention teams that already provided IPS were randomised to receive motivational interviewing training for clinicians, focused on attitudinal barriers to employment. The trial was registered with the International Standard Randomised Controlled Trial Register (ISRCTN71943786). Results Of 300 eligible participants, 159 consented to the research. Occupational outcomes were obtained for 134 patients (85%) at 12-month follow-up. More patients in the intervention teams than in the IPS-only teams achieved employment by 12 months (29/68 v. 12/66). A random effects logistic regression accounting for clustering by care coordinator, and adjusted for participants’ gender, ethnicity, educational and employment history and clinical status scores, confirmed superiority of the intervention (odds ratio = 4.3, 95% CI 1.5-16.6). Conclusions Employment outcomes were enhanced by addressing clinicians’ ambivalence about their patients returning to work.

Athletic groin pain (part 2): a prospective cohort study on the biomechanical evaluation of change of direction identifies three clusters of movement patterns

Background: Athletic groin pain (AGP) is prevalent in sports involving repeated accelerations, decelerations, kicking and change-of-direction movements. Clinical and radiological examinations lack the ability to assess pathomechanics of AGP, but three-dimensional biomechanical movement analysis may be an important innovation. Aim: The primary aim was to describe and analyse movements used by patients with AGP during a maximum effort change-of-direction task. The secondary aim was to determine if specific anatomical diagnoses were related to a distinct movement strategy. Methods: 322 athletes with a current symptom of chronic AGP participated. Structured and standardised clinical assessments and radiological examinations were performed on all participants. Additionally, each participant performed multiple repetitions of a planned maximum effort change-of-direction task during which whole body kinematics were recorded. Kinematic and kinetic data were examined using continuous waveform analysis techniques in combination with a subgroup design that used gap statistic and hierarchical clustering. Results: Three subgroups (clusters) were identified. Kinematic and kinetic measures of the clusters differed strongly in patterns observed in thorax, pelvis, hip, knee and ankle. Cluster 1 (40%) was characterised by increased ankle eversion, external rotation and knee internal rotation and greater knee work. Cluster 2 (15%) was characterised by increased hip flexion, pelvis contralateral drop, thorax tilt and increased hip work. Cluster 3 (45%) was characterised by high ankle dorsiflexion, thorax contralateral drop, ankle work and prolonged ground contact time. No correlation was observed between movement clusters and clinically palpated location of the participant's pain. Conclusions: We identified three distinct movement strategies among athletes with long-standing groin pain during a maximum effort change-of-direction task. These movement strategies were not related to clinical assessment findings but highlighted targets for rehabilitation in response to possible propagative mechanisms. Trial registration number NCT02437942, pre results.

Generalized cluster states based on finite groups

We define generalized cluster states based on finite group algebras in analogy to the generalization of the toric code to the Kitaev quantum double models. We do this by showing a general correspondence between systems with CSS structure and finite group algebras, and applying this to the cluster states to derive their generalization. We then investigate properties of these states including their projected entangled pair state representations, global symmetries, and relationship to the Kitaev quantum double models. We also discuss possible applications of these states.