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.

Understanding the relationship between the Talented Twenty program and college aspirations for high ranking students at a high priority school

Percentage plans such as the Talented Twenty program purport to assist and motivate high ranking students to attend college and grant access to higher education. This type of plan is particularly important to students enrolled in high priority schools who might not view themselves as potential college students. This study examined the relationship between Florida’s Talented Twenty program that begins intervention with juniors and the college aspirations for high ranking students at a high priority school. Numerous studies have established that increased levels of education lead to higher salaries, career mobility, and an increased quality of life (e.g., Bowen, 1997; Leslie & Brinkman 1988; Pascarella & Terenzini, 1991, Swail, 2000). Given the importance of students’ decisions regarding whether or not they will attend college, understanding how and when they make decisions about attending college is important for them, their parents, advisors, and educational administrators. This research examined students’ perceptions and insights via interviews. The overarching research question was: How do high ranking high school students attending a high priority school in a south Florida district perceive their college opportunities? Sixteen high ranking students, grades nine – 12 from a high priority school in Miami-Dade County participated in the study. Participants were identified by a school counselor and individual semi structured interviews were conducted at the school. Utilizing a student development theoretical framework developed by Hossler and Gallagher (1987) that centered on students’ predisposition, search strategies and choices, data were organized and emergent themes analyzed. The analysis of the data revealed that in alignment with the framework (a) parents were the strongest influence in the development of these students’ college aspirations, (b) these students formalized their higher education plans between eighth and 10th grade, (c) these students actively engaged in academic searches and learning opportunities that increased their chances to be admitted into college, and (d) there was no relationship between knowledge regarding the Talented Twenty program and their educational decisions. This study’s findings suggest that interventions and programs intended to influence the educational aspirations of students are more likely to succeed if they take place by the eighth or ninth grade.

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.

Absolute abundances of dinoflagellate cysts in surface sediment samples from four sites: Lycopodium marker-grain method

Absolute abundances (concentrations) of dinoflagellate cysts are often determined through the addition of Lycopodium clavatum marker-grains as a spike to a sample before palynological processing. An inter-laboratory calibration exercise was set up in order to test the comparability of results obtained in different laboratories, each using its own preparation method. Each of the 23 laboratories received the same amount of homogenized splits of four Quaternary sediment samples. The samples originate from different localities and consisted of a variety of lithologies. Dinoflagellate cysts were extracted and counted, and relative and absolute abundances were calculated. The relative abundances proved to be fairly reproducible, notwithstanding a need for taxonomic calibration. By contrast, excessive loss of Lycopodium spores during sample preparation resulted in non-reproducibility of absolute abundances. Use of oxidation, KOH, warm acids, acetolysis, mesh sizes larger than 15 µm and long ultrasonication (> 1 min) must be avoided to determine reproducible absolute abundances. The results of this work therefore indicate that the dinoflagellate cyst worker should make a choice between using the proposed standard method which circumvents critical steps, adding Lycopodium tablets at the end of the preparation and using an alternative method.

Nematode absolute densities and genus counts from four stations near the Antarctic Peninsula, collected with a multicorer device during POLARSTERN cruise ANT-XXIX/3 in January-March 2013

Marine free-living nematode communities were studied at similar depths (~500m) at two sides of the Antarctic Peninsula, characterised by different environmental and oceanographic conditions. At the Weddell Sea side, benthic communities are influenced by cold deep-water formation and seasonal sea-ice conditions, whereas the Drake Passage side experiences milder oceanic conditions and strong dynamics of the Antarctic Circumpolar Current. Surface primary productivity contrasted with observed benthic pigment patterns and varied according to the area studied: chlorophyll a concentrations (as a proxy for primary production) were high in the Weddell Sea sediments, but low in the surface waters above; this pattern was reversed in the Drake Passage. Differences between areas were largely mirrored by the nematode communities: nematode densities peaked in Weddell stations and showed deeper vertical occurrence in the sediment, associated with deeper penetration of chlorophyll a. Generic composition did not differ markedly between both areas, but rather showed distinct community shifts with depth in the sediment.

Comparison of available measurements of the absolute air-fluorescence yield and determination of its global average value

Experimental results of the absolute air-fluorescence yield are given very often in different units (photons/MeV or photons/m) and for different wavelength intervals. In this work we present a comparison of available results normalized to its value in photons/MeV for the 337 nm band at 1013 hPa and 293 K. The conversion of photons/m to photons/MeV requires an accurate determination of the energy deposited by the electrons in the field of view of the experimental set-up. We have calculated the energy deposition for each experiment by means of a detailed Monte Carlo simulation and the results have been compared with those assumed or calculated by the authors. As a result, corrections to the reported fluorescence yields are proposed. These corrections improve the compatibility between measurements in such a way that a reliable average value with uncertainty at the level of 5% is obtained.

Absolute calibration and characterization of the multiband imaging photometer for Spitzer. I. The stellar calibrator sample and the 24 μm calibration

We present the stellar calibrator sample and the conversion from instrumental to physical units for the 24 μm channel of the Multiband Imaging Photometer for Spitzer (MIPS). The primary calibrators are A stars, and the calibration factor based on those stars is 4.54 × 10^-2 MJy sr^–1 (DN/s)^–1, with a nominal uncertainty of 2%. We discuss the data reduction procedures required to attain this accuracy; without these procedures, the calibration factor obtained using the automated pipeline at the Spitzer Science Center is 1.6% ± 0.6% lower. We extend this work to predict 24 μm flux densities for a sample of 238 stars that covers a larger range of flux densities and spectral types. We present a total of 348 measurements of 141 stars at 24 μm. This sample covers a factor of ~460 in 24 μm flux density, from 8.6 mJy up to 4.0 Jy. We show that the calibration is linear over that range with respect to target flux and background level. The calibration is based on observations made using 3 s exposures; a preliminary analysis shows that the calibration factor may be 1% and 2% lower for 10 and 30 s exposures, respectively. We also demonstrate that the calibration is very stable: over the course of the mission, repeated measurements of our routine calibrator, HD 159330, show a rms scatter of only 0.4%. Finally, we show that the point-spread function (PSF) is well measured and allows us to calibrate extended sources accurately; Infrared Astronomy Satellite (IRAS) and MIPS measurements of a sample of nearby galaxies are identical within the uncertainties.

Asymmetric Synthesis and Absolute Configuration of (+)- and (–)-Perhexiline

Peer reviewed

Asymmetric Synthesis and Absolute Configuration of (+)- and (–)-Perhexiline

Peer reviewed

Investigation of factors driving the costs of operating the 2020 Irish power system with large-scale wind generation

The main goal of this work is to determine the true cost incurred by the Republic of Ireland and Northern Ireland in order to meet their EU renewable electricity targets. The primary all-island of Ireland policy goal is that 40% of electricity will come from renewable sources in 2020. From this it is expected that wind generation on the Irish electricity system will be in the region of 32-37% of total generation. This leads to issues resulting from wind energy being a non-synchronous, unpredictable and variable source of energy use on a scale never seen before for a single synchronous system. If changes are not made to traditional operational practices, the efficient running of the electricity system will be directly affected by these issues in the coming years. Using models of the electricity system for the all-island grid of Ireland, the effects of high wind energy penetration expected to be present in 2020 are examined. These models were developed using a unit commitment, economic dispatch tool called PLEXOS which allows for a detailed representation of the electricity system to be achieved down to individual generator level. These models replicate the true running of the electricity system through use of day-ahead scheduling and semi-relaxed use of these schedules that reflects the Transmission System Operator's of real time decision making on dispatch. In addition, it carefully considers other non-wind priority dispatch generation technologies that have an effect on the overall system. In the models developed, three main issues associated with wind energy integration were selected to be examined in detail to determine the sensitivity of assumptions presented in other studies. These three issues include wind energy's non-synchronous nature, its variability and spatial correlation, and its unpredictability. This leads to an examination of the effects in three areas: the need for system operation constraints required for system security; different onshore to offshore ratios of installed wind energy; and the degrees of accuracy in wind energy forecasting. Each of these areas directly impact the way in which the electricity system is run as they address each of the three issues associated with wind energy stated above, respectively. It is shown that assumptions in these three areas have a large effect on the results in terms of total generation costs, wind curtailment and generator technology type dispatch. In particular accounting for these issues has resulted in wind curtailment being predicted in much larger quantities than had been previously reported. This would have a large effect on wind energy companies because it is already a very low profit margin industry. Results from this work have shown that the relaxation of system operation constraints is crucial to the economic running of the electricity system with large improvements shown in the reduction of wind curtailment and system generation costs. There are clear benefits in having a proportion of the wind installed offshore in Ireland which would help to reduce variability of wind energy generation on the system and therefore reduce wind curtailment. With envisaged future improvements in day-ahead wind forecasting from 8% to 4% mean absolute error, there are potential reductions in wind curtailment system costs and open cycle gas turbine usage. This work illustrates the consequences of assumptions in the areas of system operation constraints, onshore/offshore installed wind capacities and accuracy in wind forecasting to better inform the true costs associated with running Ireland's changing electricity system as it continues to decarbonise into the near future. This work also proposes to illustrate, through the use of Ireland as a case study, the effects that will become ever more prevalent in other synchronous systems as they pursue a path of increasing renewable energy generation.

Personalized absolute benefit of statin treatment for primary or secondary prevention of vascular disease in individual elderly patients

Objective: To estimate the absolute treatment effect of statin therapy on major adverse cardiovascular events (MACE; myocardial infarction, stroke and vascular death) for the individual patient aged C70 years. Methods: Prediction models for MACE were derived in patients aged C70 years with (n = 2550) and without (n = 3253) vascular disease from the ‘‘PROspective Study of Pravastatin in Elderly at Risk’’ (PROSPER) trial and validated in the ‘‘Secondary Manifestations of ARTerial disease’’ (SMART) cohort study (n = 1442) and the ‘‘Anglo-Scandinavian Cardiac Outcomes Trial-Lipid Lowering Arm’’ (ASCOT-LLA) trial (n = 1893), respectively, using competing risk analysis. Prespecified predictors were various clinical characteristics including statin treatment. Individual absolute risk reductions (ARRs) for MACE in 5 and 10 years were estimated by subtracting ontreatment from off-treatment risk. Results: Individual ARRs were higher in elderly patients with vascular disease [5-year ARRs: median 5.1 %, interquartile range (IQR) 4.0–6.2 %, 10-year ARRs: median 7.8 %, IQR 6.8–8.6 %] than in patients without vascular disease (5-year ARRs: median 1.7 %, IQR 1.3–2.1 %, 10-year ARRs: 2.9 %, IQR 2.3–3.6 %). Ninetyeight percent of patients with vascular disease had a 5-year ARR C2.0 %, compared to 31 % of patients without vascular disease. Conclusions: With a multivariable prediction model the absolute treatment effect of a statin on MACE for individual elderly patients with and without vascular disease can be quantified. Because of high ARRs, treating all patients is more beneficial than prediction-based treatment for secondary prevention of MACE. For primary prevention of MACE, the prediction model can be used to identify those patients who benefit meaningfully from statin therapy.