929 resultados para Nucleophilic additions


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In the ancient and acidic Ultisol soils of the Southern Piedmont, USA, we studied changes in trace element biogeochemistry over four decades, a period during which formerly cultivated cotton fields were planted with pine seedlings that grew into mature forest stands. In 16 permanent plots, we estimated 40-year accumulations of trace elements in forest biomass and O horizons (between 1957 and 1997), and changes in bioavailable soil fractions indexed by extractions of 0.05 mol/L HCl and 0.2 mol/L acid ammonium oxalate (AAO). Element accumulations in 40-year tree biomass plus O horizons totaled 0.9, 2.9, 4.8, 49.6, and 501.3 kg/ha for Cu, B, Zn, Mn, and Fe, respectively. In response to this forest development, samples of the upper 0.6-m of mineral soil archived in 1962 and 1997 followed one of three patterns. (1) Extractable B and Mn were significantly depleted, by -4.1 and -57.7 kg/ha with AAO, depletions comparable to accumulations in biomass plus O horizons, 2.9 and 49.6 kg/ha, respectively. Tree uptake of B and Mn from mineral soil greatly outpaced resupplies from atmospheric deposition, mineral weathering, and deep-root uptake. (2) Extractable Zn and Cu changed little during forest growth, indicating that nutrient resupplies kept pace with accumulations by the aggrading forest. (3) Oxalate-extractable Fe increased substantially during forest growth, by 275.8 kg/ha, about 10-fold more than accumulations in tree biomass (28.7 kg/ha). The large increases in AAO-extractable Fe in surficial 0.35-m mineral soils were accompanied by substantial accretions of Fe in the forest's O horizon, by 473 kg/ha, amounts that dwarfed inputs via litterfall and canopy throughfall, indicating that forest Fe cycling is qualitatively different from that of other macro- and micronutrients. Bioturbation of surficial forest soil layers cannot account for these fractions and transformations of Fe, and we hypothesize that the secondary forest's large inputs of organic additions over four decades has fundamentally altered soil Fe oxides, potentially altering the bioavailability and retention of macro- and micronutrients, contaminants, and organic matter itself. The wide range of responses among the ecosystem's trace elements illustrates the great dynamics of the soil system over time scales of decades.

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Using a natural gradient of dissolved organic carbon (DOC) source and concentration in rivers of northern Florida, we investigated how terrestrially-derived DOC affects denitrification rates in river sediments. Specifically, we examined if the higher concentrations of DOC in blackwater rivers stimulate denitrification, or whether such terrestrially-derived DOC supports lower denitrification rates because (1) it is less labile than DOC from aquatic primary production; whether (2) terrestrial DOC directly inhibits denitrification via biochemical mechanisms; and/or whether (3) terrestrial DOC indirectly inhibits denitrification via reduced light availability to-and thus DOC exudation by-aquatic primary producers. We differentiated among these mechanisms using laboratory denitrification assays that subjected river sediments to factorial amendments of NO3- and dextrose, humic acid dosing, and cross-incubations of sediments and water from different river sources. DOC from terrestrial sources neither depressed nor stimulated denitrification rates, indicating low lability of this DOC but no direct inhibition; humic acid additions similarly did not affect denitrification rates. However, responses to addition of labile C increased with long-term average DOC concentration, which supports the hypothesis that terrestrial DOC indirectly inhibits denitrification via decreased autochthonous production. Observed and future changes in DOC concentration may therefore reduce the ability of inland waterways to remove reactive nitrogen. © 2013 Springer Science+Business Media New York.

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Intensive archaeological investigation was undertaken on an urban backlot in Annapolis, Maryland. Fieldwork was conducted on behalf of Historic Annapolis Foundation for the property's owners, King and Cornwall, Inc. Supplemental documentary research, an evaluation of existing conditions on the property, and below-ground excavation of a 35 X 70 ft. urban backlot were conducted. While the project was not a Section 106 compliance effort, the field methods and rationale for the site's investigation are comparable to those of standard Phase II site evaluations. Historical documentation attested to the fact that the 22 West Street Backlot, located along the western most edge of the Historic District of Annapolis, Maryland, had seen development and occupation since the first quarter of the eighteenth century. A substantial brick structure was known to have occupied the property in a series of altered forms for much of that period. This structure served a variety of purposes over time: a private residence in the eighteenth century, a boarding house in the nineteenth century (known as the National Hotel), a duplex in the early twentieth century, half of which remained in use until the structure was entirely razed in the 1970s after destruction by fire. Recovery and analysis of site formation processes (i.e., both cultural and natural transformations of the buried remains) indicated that sections of the site were disturbed to a depth of six feet. In contrast to what initially seemed a poor prognosis for site integrity, other areas of the backlot revealed numerous intact historical features and deposits. Structural remains from the dwelling and its associated outbuildings, additions, and attendant trash deposits were recovered. What was initiated as a program of limited testing evolved into a larger-scale undertaking that made use of largely hand-excavated units in conjunction with machine-assisted stripping of areas demonstrated to contain from four to six-foot deep sterile layers of fill. The current investigations provided a window into a portion of the city and period in its history not documented archaeologically. Moreover, this project provided valuable insight into the archaeology of the homelot within a lightly industrialized, urban context. Evidence was recovered of shifts in the layout and arrangement of the houselot as well as changing relations between individuals and the workplace--all within an urban context--an issue defined elsewhere in the archaeological literature as a significant one. No further investigations are recommended for the site, however, further analysis and interpretation of materials recovered are ongoing. In the event that the site were to undergo development, monitoring of any construction activity is recommended.

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OBJECTIVE: The research studied the status of hospital librarians and library services to better inform the Medical Library Association's advocacy activities. METHODS: The Vital Pathways Survey Subcommittee of the Task Force on Vital Pathways for Hospital Librarians distributed a web-based survey to hospital librarians and academic health sciences library directors. The survey results were compared to data collected in a 1989 survey of hospital libraries by the American Hospital Association in order to identify any trends in hospital libraries, roles of librarians, and library services. A web-based hospital library report form based on the survey questions was also developed to more quickly identify changes in the status of hospital libraries on an ongoing basis. RESULTS: The greatest change in library services between 1989 and 2005/06 was in the area of access to information, with 40% more of the respondents providing access to commercial online services, 100% more providing access to Internet resources, and 28% more providing training in database searching and use of information resources. Twenty-nine percent (n = 587) of the 2005/06 respondents reported a decrease in staff over the last 5 years. CONCLUSIONS: Survey data support reported trends of consolidation of hospitals and hospital libraries and additions of new services. These services have likely required librarians to acquire new skills. It is hoped that future surveys will be undertaken to continue to study these trends.

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© 2015 by the authors.The future climate of the southeastern USA is predicted to be warmer, drier and more variable in rainfall, which may increase drought frequency and intensity. Loblolly pine (Pinus taeda) is the most important commercial tree species in the world and is planted on ~11 million ha within its native range in the southeastern USA. A regional study was installed to evaluate effects of decreased rainfall and nutrient additions on loblolly pine plantation productivity and physiology. Four locations were established to capture the range-wide variability of soil and climate. Treatments were initiated in 2012 and consisted of a factorial combination of throughfall reduction (approximate 30% reduction) and fertilization (complete suite of nutrients). Tree and stand growth were measured at each site. Results after two growing seasons indicate a positive but variable response of fertilization on stand volume increment at all four sites and a negative effect of throughfall reduction at two sites. Data will be used to produce robust process model parameterizations useful for simulating loblolly pine growth and function under future, novel climate and management scenarios. The resulting improved models will provide support for developing management strategies to increase pine plantation productivity and carbon sequestration under a changing climate.

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Cotoneaster pannosus (Rosaceae), an ornamental shrub native to China, is reported for the first time in Tarragona Province (Catalonia, Spain). Data on demography and accompanying species for the new locality are provided, in addition to a chrorological update at nation level.

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Fast Repetition Rate fluorometry (FRRf) measurements of phytoplankton photophysiology from an across-basin South Atlantic cruise (as part of the GEOTRACES programme) characterised two dominant ecophysiological regimes which were interpreted on the basis of nutrient limitation. South of the South Subtropical Convergence (SSTC) in the northern sub-Antarctic sector of the Antarctic Circumpolar Current (ACC) in the Eastern Atlantic Basin, waters are characterised by elevated chlorophyll concentrations, a dominance by larger phytoplankton cells, and low apparent photochemical efficiency (F-v/F-m). Shipboard 24 h iron (Fe) addition incubation experiments confirmed that Fe stress was primarily responsible for the low F-v/F-m, with Fe addition to these waters, either within the artificial bottle additions or naturally occurring downstream enrichment from Gough Island, significantly increasing F-v/F-m values. To the north of the SSTC at the southern boundary of the South Atlantic Gyre, phytoplankton are characterised by high values of F-v/F-m which, coupled with the low macronutrient concentrations and increased presence of picocyanobacteria, are interpreted as conditions of Fe replete, balanced macronutrient-limited growth. Spatial correlation was found between F-v/F-m and Fe: nitrate ratios, supporting the suggestion that the relative supply ratios of these two nutrients can control patterns of limitation and consequently the ecophysiology of phytoplankton in subtropical gyre and ACC regimes.

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A three dimensional hydrodynamic model with a coupled carbonate speciation sub-model is used to simulate large additions of CO2into the North Sea, representing leakages at potential carbon sequestration sites. A range of leakage scenarios are conducted at two distinct release sites, allowing an analysis of the seasonal, inter-annual and spatial variability of impacts to the marine ecosystem. Seasonally stratified regions are shown to be more vulnerable to CO2release during the summer as the added CO2remains trapped beneath the thermocline, preventing outgasing to the atmosphere. On average, CO2 injected into the northern North Sea is shown to reside within the water column twice as long as an equivalent addition in the southern North Sea before reaching the atmosphere. Short-term leakages of 5000 tonnes CO2over a single day result in substantial acidification at the release sites (up to -1.92 pH units), with significant perturbations (greater than 0.1 pH units) generally confined to a 10 km radius. Long-term CO2leakages sustained for a year may result in extensive plumes of acidified seawater, carried by major advective pathways. Whilst such scenarios could be harmful to marine biota over confined spatial scales, continued unmitigated CO2emissions from fossil fuels are predicted to result in greater and more long-lived perturbations to the carbonate system over the next few decades.

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The effects of ocean acidification (OA) on nitrous oxide (N2O) production and on the community composition of ammonium oxidizing archaea (AOA) were examined in the northern and southern sub-polar and polar Atlantic Ocean. Two research cruises were performed during June 2012 between the North Sea and Arctic Greenland and Barent Seas, and in January–February 2013 to the Antarctic Scotia Sea. Seven stations were occupied in all during which shipboard experimental manipulations of the carbonate chemistry were performed through additions of NaHCO3−+HCl in order to examine the impact of short-term (48 h for N2O and between 96 and 168 h for AOA) exposure to control and elevated conditions of OA. During each experiment, triplicate incubations were performed at ambient conditions and at 3 lowered levels of pH which varied between 0.06 and 0.4 units according to the total scale and which were targeted at CO2 partial pressures of ~500, 750 and 1000 µatm. The AOA assemblage in both Arctic and Antarctic regions was dominated by two major archetypes that represent the marine AOA clades most often detected in seawater. There were no significant changes in AOA assemblage composition between the beginning and end of the incubation experiments. N2O production was sensitive to decreasing pHT at all stations and decreased by between 2.4% and 44% with reduced pHT values of between 0.06 and 0.4. The reduction in N2O yield from nitrification was directly related to a decrease of between 28% and 67% in available NH3 as a result of the pH driven shift in the NH3:NH4+ equilibrium. The maximum reduction in N2O production at conditions projected for the end of the 21st century was estimated to be 0.82 Tg N y−1.

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As a continuation of previous research on the naturalization of non-native vascular plants in the Iberian Peninsula new chorological data are presented for 16 xenophytes recorded between 2010 and 2014, mostly in the provinces of Huelva and Barcelona (Spain) and in the Algarve and Estremadura (Portugal). For each taxon details about distribution, habitats occupied, previous records, degree of naturalization, etc. are provided. Lachenalia bulbifera and Cyperus albostriatus are probably reported for the first time in the wild in Europe, as are Gamochaeta filaginea, and Dysphania anthelmintica and Oenothera lindheimeri for Portugal and Spain respectively. Cosmos bipinnatus is cited as a novelty for the Algarve (Portugal). Newly reported or confirmed for the province of Huelva are: Amaranthus hypochondriacus, Epilobium brachycarpum, Nephrolepis cordifolia, Ficus microcarpa, Tamarix parviflora and Tamarix ramosissima, while Atriplex semibaccata, Chloris truncata, and Elymus elongatus subsp. ponticus are new for Barcelona. Finally, Passiflora caerulea is a novelty for both Barcelona and Huelva provinces.

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Aminolevulinic acid (ALA) stability within topical formulations intended for photodynamic therapy (PDT) is poor due to dimerisation to pyrazine-2,5-dipropionic acid (PY). Most strategies to improve stability use low pH vehicles, which can cause cutaneous irritancy. To overcome this problem, a novel approach is investigated that uses a non-aqueous vehicle to retard proton-induced charge separation across the 4-carbonyl group on ALA and lessen nucleophilic attack that leads to condensation dimerisation. Bioadhesive anhydrous vehicles based on methylvinylether-maleic anhydride copolymer patches and poly(ethyleneglycol) or glycerol thickened poly(acrylic acid) gels were formulated. ALA stability fell below pharmaceutically acceptable levels after 6 months, with bioadhesive patches stored at 5°C demonstrating the best stability by maintaining 86.2% of their original loading. Glycerol-based gels maintained 40.2% in similar conditions. However, ALA loss did not correspond to expected increases in PY, indicating the presence of another degradative process that prevented dimerisation. Nuclear magnetic resonance (NMR) analysis was inconclusive in respect of the mechanism observed in the patch system, but showed clearly that an esterification reaction involving ALA and both glycerol and poly(ethyleneglycol) was occurring. This was especially marked in the glycerol gels, where only 2.21% of the total expected PY was detected after 204 days at 5°C. Non-specific esterase hydrolysis demonstrated that ALA was recoverable from the gel systems, further supporting esterified binding within the gel matrices. It is conceivable that skin esterases could duplicate this finding upon topical application of the gel and convert these derivatives back to ALA in situ, provided skin penetration is not affected adversely.

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Density functional calculations of the structure, potential energy surface and reactivity for organic systems closely related to bisphenol-A-polycarbonate (BPA-PC) provide the basis for a model describing the ring-opening polymerization of its cyclic oligomers by nucleophilic molecules. Monte Carlo simulations using this model show a strong tendency to polymerize that is increased by increasing density and temperature, and is greater in 3D than in 2D. Entropy in the distribution of inter-particle bonds is the driving force for chain formation. (C) 2002 Elsevier Science B.V. All rights reserved.

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In this paper the claim for the market for a new business management to ensure the presence of women in decision -making to respond to new social needs addressed. Thus, this paper analyzes the influence of gender diversity of the directors on the profitability and the level of debt for a sample of 5,199 Spanish cooperatives. Unlike capitalist societies, these organizations have a number of peculiarities in their government, and that the partners are themselves major time, agents and customers. The study focuses on the Spanish context, where there is an open debate on the importance of women's business management, as in other countries, driven by the proliferation of legislation on gender equality, being, in addition, Spain, the pioneer in having specific legislation on Social Economy. The results show that cooperatives with greater female representation in theirs Boards have higher profitability. On the other hand, those Boards with a higher percentage of women show a lower level of indebtedness.

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Volume III of the new eleven-volume edition of Milton's Complete Works provides a definitive scholarly edition of all of Milton's shorter poems in English, Latin, Italian, and Greek, as well as his Mask, taken from both published and manuscript sources. It includes his 1645 Poems complete with all prefatory materials, thus illuminating the ways in which author, publisher, and print shop shaped this volume. It then presents all the new poems added in the 1673 edition (with the new Table of Contents), as well as the poems omitted from both editions. A careful collation of textual variants among these sources as well as the 1637 anonymous publication of Milton's Mask is provided. The Bridgewater manuscript of Milton's Mask (probably close to the acting version) and his working copy from the Trinity Manuscript, with its many alterations and additions, are transcribed in their entirety, so that the various versions may be compared and studied. 

A special feature of this edition is a new translation of Milton's many Latin and Greek poems that is both accurate and attentive to their literary qualities. This is augmented by a detailed and comprehensive commentary that highlights classical, vernacular, and neo-Latin parallels. A poetic translation of Milton's six Italian sonnets and Canzone is also supplied. In addition, the Appendices contain all the versions of Milton's shorter poems in all the contemporary manuscript and printed sources, so they may be examined in relation to their specific contexts. The transcription of all the versions of Milton's poems in the Trinity Manuscript allows in several cases, notably 'Lycidas' and 'At a Solemn Music,' for examination of the evolution of these poems as Milton weighed choiced of diction and sound qualities, enabling further understanding of his poetic practices. 

Barbara Lewalski is responsible for text, textual apparatus, and commentary pertaining to the vernacular poems in all sections of this edition including the appendices, and manuscript transcriptions (with the exception of A Maske), as well as the Occasions, Vernacular Poems,and Textual Introductions. Estelle Haan is responsible for text, textual apparatus, and commentary for the Poemata in all sections of this edition,and for the Poemata Introduction. She has also provided all translations from Latin, Italian, and Greek in the Testimonia, Poemata, and associated commentary, and transcriptions of the BL Damon, the Bodleian AdJoannem Rousium, and A Maske from the Trinity and Bridgewater manuscripts. Andrew McNeillie has provided poetic translations for Milton’s Italian sonnets, and Jason Rosenblatt has provided some Hebrew text and commentary pertaining to Milton’s Psalm translations.John Cunningham has transcribed Henry Lawes’ music for Milton’s masque, with commentary (Appendix E). Biblical references are taken from the King James (Authorized) Version.

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OBJECTIVES: This study reports the development, characterisation and microbiological testing of surface-modified polyvinylchloride (PVC) films for the purpose of reducing bacterial adherence.

METHODS: Irreversible covalent surface modification was achieved via nucleophilic substitution of fluorinated thiol-terminated compounds onto the polymer backbone. Four fluorinated modifiers, 2,3,5,6-tetrafluorothiophenol (TFTP), 4-(trifluoromethyl)thiophenol (TFMTP), 3,5-bis(trifluoromethyl)benzenethiol (BTFMBT) and 3,3,4,4,5,5,6,6,7, 7,8,8,9,9,10,10,10-heptadecafluoro-decane-1-thiol (HDFDT), were investigated. Modification was confirmed using attenuated total reflectance infrared spectroscopy; Raman mapping demonstrated that modification was homogenous on the macroscopic scale. The influence of fluorination on surface hydrophobicity was studied by contact angle analysis. The effect on microbial adherence was examined using Pseudomonas aeruginosa and Staphylococcus aureus.

KEY FINDINGS: The resultant changes in contact angle relative to control PVC ranged from -4 degrees to +14 degrees . In all cases, adherence of P. aeruginosa and S. aureus was significantly reduced relative to control PVC, with adherence levels ranging from 62% and 51% for TFTP-modified PVC to 32% and 7% for TFMTP-modified PVC.

CONCLUSIONS: These results demonstrate an important method in reducing the incidence of bacterial infection in PVC medical devices without compromising mechanical properties.