34 resultados para anomalous Eu3 5D0->F-7(0) transition
em CentAUR: Central Archive University of Reading - UK
Resumo:
Seasonal sea-surface temperaturevariability for the Neoglacial (3300–2500 BP) and Roman WarmPeriod (RWP; 2500–1600 BP), which correspond to the Bronze and Iron Ages, respectively, was estimated using oxygen isotope ratios obtained from high-resolution samples micromilled from radiocarbon-dated, archaeological limpet (Patella vulgata) shells. The coldest winter months recorded in Neoglacial shells averaged 6.6 ± 0.3 °C, and the warmest summer months averaged 14.7 ± 0.4 °C. One Neoglacial shell captured a year without a summer, which may have resulted from a dust veil from a volcanic eruption in the Katla volcanic system in Iceland. RWP shells record average winter and summer monthly temperatures of 6.3 ± 0.1 °C and 13.3 ± 0.3 °C, respectively. These results capture a cooling transition from the Neoglacial to RWP, which is further supported by earlier studies of pine history in Scotland, pollen type analyses in northeast Scotland, and European glacial events. The cooling transition observed at the boundary between the Neoglacial and RWP in our study also agrees with the abrupt climate deterioration at 2800–2700 BP (also referred to as the Subboreal/Subatlantic transition) and therefore may have been driven by decreased solar radiation and weakened North Atlantic Oscillation conditions.
Resumo:
A set of lysimeter based experiments was carried out during 2000/01 to evaluate the impact of soil type and grassland management on potassium (K) leaching. The effects of (1) four soil textures (sand, loam, loam over chalk and clay), (2) grazing and cutting (with farmyard manure application), and (3) K applied as inorganic fertilizer, dairy slurry or a mixture of both sources were tested. Total K losses in the clay soil were more than twice those in the sand soil (13 and 6 kg K ha(-1), respectively) because of the development of preferential flow in the clay soil. They were also greater in the cut treatment than in the grazed treatment (82 and 51 kg K ha(-1), respectively; P less than or equal to0.01), associated with a 63% increase of K concentration in the leachates from the former (6.7 +/- 0.28 and 4.1 +/- 0.22 mg K L-1 for cut and grazed, respectively; P less than or equal to0.01) because of the K input from the farmyard manure. The source of fertilizer did not affect total K losses or the average K concentration in the leachates (P >0.05), but it changed the pattern of these over time.
Resumo:
The effect of sesquioxides on the mechanisms of chemical reactions that govern the transformation between exchangeable potassium (Kex) and non-exchangeable K (Knex) was studied on acid tropical soils from Colombia: Caribia with predominantly 2 : 1 clay minerals and High Terrace with predominantly 1 : 1 clay minerals and sesquioxides. Illite and vermiculite are the main clay minerals in Caribia followed by kaolinite, gibbsite, and plagioclase, and kaolinite is the major clay mineral in High Terrace followed by hydroxyl-Al interlayered vermiculite, quartz, and pyrophyllite. The soils have 1.8 and 0.5% of K2O, respectively. They were used either untreated or prepared by adding AlCl3 and NaOH, which produced aluminum hydroxide. The soils were percolated continuously with 10mM NH4OAc at pH 7.0 and 10 mM CaCl2 at pH 5.8 for 120 h at 6 mL h(-1) to examine the release of Kex and Knex. In the untreated soils, NH4+ and Ca-2(+) released the same amounts of Kex from Caribia, whereas NH4+ released about twice as much Kex as Ca2+ from High Terrace. This study proposes that the small ionic size of NH4+ (0.54nm) enables it to enter more easily into the K sites at the broken edges of the kaolinite where Ca2+ (0.96 nm) cannot have access. As expected for a soil dominated by 2 : 1 clay minerals, Ca2+ caused Knex to be released from Caribia with no release by NH4+. No Knex was released by either ion from High Terrace. After treatment with aluminum hydroxide, K release from the exchangeable fraction was reduced in Caribia due to the blocking of the exchange sites but release of Knex was not affected. The treatment increased the amount of Kex released from the High Terrace soil and the release of Knex remained negligible although with Ca2+ the distinction between Kex and Knex was unclear. The increase in Kex was attributed to the initially acidic conditions produced by adding AlCl3 which may have dissolved interlayered aluminum hydroxide from the vermiculite present, thus exposing trapped K as exchangeable K. The subsequent precipitation of aluminum hydroxide when NaOH was added did not interfere with the release of this K, and so was probably formed mostly on the surface of the dominant kaolinite. Measurement of availability of K by standard methods using NH4 salts could result in overestimates in High Terrace and this may be a more general shortcoming of the methods in kaolinitic soils.
Resumo:
Objectives: To assess the impact of a closed-loop electronic prescribing, automated dispensing, barcode patient identification and electronic medication administration record (EMAR) system on prescribing and administration errors, confirmation of patient identity before administration, and staff time. Design, setting and participants: Before-and-after study in a surgical ward of a teaching hospital, involving patients and staff of that ward. Intervention: Closed-loop electronic prescribing, automated dispensing, barcode patient identification and EMAR system. Main outcome measures: Percentage of new medication orders with a prescribing error, percentage of doses with medication administration errors (MAEs) and percentage given without checking patient identity. Time spent prescribing and providing a ward pharmacy service. Nursing time on medication tasks. Results: Prescribing errors were identified in 3.8% of 2450 medication orders pre-intervention and 2.0% of 2353 orders afterwards (p<0.001; χ2 test). MAEs occurred in 7.0% of 1473 non-intravenous doses pre-intervention and 4.3% of 1139 afterwards (p = 0.005; χ2 test). Patient identity was not checked for 82.6% of 1344 doses pre-intervention and 18.9% of 1291 afterwards (p<0.001; χ2 test). Medical staff required 15 s to prescribe a regular inpatient drug pre-intervention and 39 s afterwards (p = 0.03; t test). Time spent providing a ward pharmacy service increased from 68 min to 98 min each weekday (p = 0.001; t test); 22% of drug charts were unavailable pre-intervention. Time per drug administration round decreased from 50 min to 40 min (p = 0.006; t test); nursing time on medication tasks outside of drug rounds increased from 21.1% to 28.7% (p = 0.006; χ2 test). Conclusions: A closed-loop electronic prescribing, dispensing and barcode patient identification system reduced prescribing errors and MAEs, and increased confirmation of patient identity before administration. Time spent on medication-related tasks increased.
Resumo:
Time series of transports in the Agulhas region have been constructed by simulating Lagrangian drifter trajectories in a 1/10 degree two-way nested ocean model. Using these 34 year long time series it is shown that smaller (larger) Agulhas Current transport leads to larger (smaller) Indian-Atlantic inter-ocean exchange. When transport is low, the Agulhas Current detaches farther downstream from the African continental slope. Moreover, the lower inertia suppresses generation of anti-cyclonic vorticity. These two effects cause the Agulhas retroflection to move westward and enhance Agulhas leakage. In the model a 1 Sv decrease in Agulhas Current transport at 32°S results in a 0.7 ± 0.2 Sv increase in Agulhas leakage.
Resumo:
Measurements of anthropogenic tracers such as chlorofluorocarbons and tritium must be quantitatively combined with ocean general circulation models as a component of systematic model development. The authors have developed and tested an inverse method, using a Green's function, to constrain general circulation models with transient tracer data. Using this method chlorofluorocarbon-11 and -12 (CFC-11 and -12) observations are combined with a North Atlantic configuration of the Miami Isopycnic Coordinate Ocean Model with 4/3 degrees resolution. Systematic differences can be seen between the observed CFC concentrations and prior CFC fields simulated by the model. These differences are reduced by the inversion, which determines the optimal gas transfer across the air-sea interface, accounting for uncertainties in the tracer observations. After including the effects of unresolved variability in the CFC fields, the model is found to be inconsistent with the observations because the model/data misfit slightly exceeds the error estimates. By excluding observations in waters ventilated north of the Greenland-Scotland ridge (sigma (0) < 27.82 kg m(-3); shallower than about 2000 m), the fit is improved, indicating that the Nordic overflows are poorly represented in the model. Some systematic differences in the model/data residuals remain and are related, in part, to excessively deep model ventilation near Rockall and deficient ventilation in the main thermocline of the eastern subtropical gyre. Nevertheless, there do not appear to be gross errors in the basin-scale model circulation. Analysis of the CFC inventory using the constrained model suggests that the North Atlantic Ocean shallower than about 2000 m was near 20% saturated in the mid-1990s. Overall, this basin is a sink to 22% of the total atmosphere-to-ocean CFC-11 flux-twice the global average value. The average water mass formation rates over the CFC transient are 7.0 and 6.0 Sv (Sv = 10(6) m(3) s(-1)) for subtropical mode water and subpolar mode water, respectively.
Resumo:
The interactions have been investigated of puroindoline-a (Pin-a) and mixed protein systems of Pin-a and wild-type puroindoline-b (Pin-b+) or puroindoline-b mutants (G46S mutation (Pin bH) or W44R mutation (Pin-bS)) with condensed phase monolayers of an anionic phospholipid (L-α-dipalmitoylphosphatidyl-dl-glycerol (DPPG)) at the air/water interface. The interactions of the mixed systems were studied at three different concentration ratios of Pin-a:Pin-b, namely 3:1, 1:1 and 1:3 in order to establish any synergism in relation to lipid binding properties. Surface pressure measurements revealed that Pin-a interaction with DPPG monolayers led to an equilibrium surface pressure increase of 8.7 ± 0.6 mN m-1. This was less than was measured for Pin-a:Pin-b+ (9.6 to 13.4 mN m-1), but was significantly more than was measured for Pin-a:Pin-bH (4.0 to 6.2 mN m-1) or Pin-a:Pin-bS (3.8 to 6.3 mN m-1) over the complete range of concentration ratio. Consequently, surface pressure increases were shown to correlate to endosperm hardness phenotype, with puroindolines present in hard-textured wheat varieties yielding lower equilibrium surface pressure changes. Integrated amide I peak areas from corresponding external reflectance Fourier-transform infrared (ER-FTIR) spectra, used to indicate levels of protein adsorption to the lipid monolayers, showed that differences in adsorbed amount were less significant. The data therefore suggest that Pin-b mutants having single residue substitutions within their tryptophan-rich loop that are expressed in some hard-textured wheat varieties influence the degree of penetration of Pin-a and Pin-b into anionic phospholipid films. These findings highlight the key role of the tryptophan-rich loop in puroindoline-lipid interactions.
Resumo:
With the purpose of eliciting a superovulatory response, 12 adult nulliparous Boer goat does were actively immunized against a recombinant a-subunit of ovine inhibin (roIHN-alpha; two injections of 100 mg 4 weeks apart). Another 12 control Boer goat does were treated with physiological saline and acted as controls. One year later the immunized animals were boostered by the administration of another dose (100 mg) of the immunogen. Following treatment, blood samples were collected twice weekly for the periods of 16 and 12 weeks, respectively, to monitor the inhibin binding ability with the aid of a radio-tracer binding assay. Throughout the experiment, estrus detection was conducted twice daily with the aid of an aproned intact buck. From the first day after treatment to 48 h after standing estrus, ovarian activity was monitored daily by transrectal ultrasonography. On alternate estrous cycles, does were mated and 6 days later flushed transcervically to recover embryos. All goats treated with the roIHN-alpha produced antibodies reactive to the native bovine inhibin tracer-the titre increasing from 2.9 +/- 0.4 to a maximum of 21.9 +/- 2.9% binding after the second injection. The antibody titre gradually subsided over the next 16 weeks. The booster injection restored an elevated antibody titre (11.7 +/- 0.4%), which was maintained until the end of the sampling period 12 weeks later. In the control goats only trace amounts of antibody were recorded throughout the trial. In the roIHN-alpha-immunized goats the number of follicles reaching a diameter of > 4 mm was 14.6 +/- 1.2 per doe. A positive correlation was recorded between the follicle number and antibody titre (r=0.61; P < 0.01). The number of follicles ovulating per doe (6.9 +/- 0.7) followed the same tendency-however, the proportion decreased with increasing follicle numbers. A relatively weak correlation was recorded between the inhibin binding ability and number of ovulations (r=0.27; P < 0.05). In the control goats the majority (92%) of follicles exceeding 4 mm in diameter ovulated (2.5 +/- 0.1 follicles/doe). Embryo collection proved unsatisfactory (42% versus 39% recovery for immunized and control animals, respectively)-presumably because the uterine lumen of the nulliparous does was too narrow to permit effective flushing. In the group of immunized goats the occurrence of short estrous cycles (< 15 days) recorded was 34% versus only 6% in the controls. Overall, immunization of goats against roIHN-alpha led to an almost six-fold increase in number of ovarian follicles, a three-fold increase in ovulations and, despite the low recovery rate, a more than three-fold increase in ova or embryos recovered. It may be concluded that treatment of female goats with roIHN-alpha leads to an inhibin antibody response, accompanied by enhanced ovarian activity. The response was, however, accompanied by a large proportion of retained follicles and a high incidence of short estrous cycles. These problems need to be further investigated before rendering the method fit for application in embryo transfer programs in goats. (C) 2007 Elsevier B.V. All rights reserved.
Resumo:
Time-resolved studies of germylene, GeH2, generated by the 193 nm laser flash photolysis of 3,4-dimethyl-1-germacyclopent-3-ene, have been carried out to obtain rate constants for its bimolecular reactions with ethyl- and diethylgermanes in the gas phase. The reactions were studied over the pressure range 1-100 Torr with SF6 as bath gas and at five temperatures in the range 297-564 K. Only slight pressure dependences were found for GeH2 + EtGeH3 (399, 486, and 564 K). The high pressure rate constants gave the following Arrhenius parameters: for GeH2 + EtGeH3, log A = -10.75 +/- 0.08 and E-a = -6.7 +/- 0.6 kJ mol(-1); for GeH2 + Et2GeH2, log A = -10.68 +/- 0.11 and E-a = -6.95 +/- 0.80 kJ mol(-1). These are consistent with fast, near collision-controlled, association processes at 298 K. RRKM modeling calculations are, for the most part, consistent with the observed pressure dependence of GeH2 + EtGeH3. The ethyl substituent effects have been extracted from these results and are much larger than the analogous methyl substituent effects in the SiH2 + methylsilane reaction series. This is consistent with a mechanistic model for Ge-H insertion in which the intermediate complex has a sizable secondary barrier to rearrangement.
Resumo:
Resistant strains of Plasmodium falciparum and the unavailability of useful antimalarial vaccines reinforce the need to develop new efficacious antimalarials. This study details a pharmacophore model that has been used to identify a potent, soluble, orally bioavailable antimalarial bisquinoline, metaquine (N,N'-bis(7-chloroquinolin-4-yl)benzene-1,3-diamine) (dihydrochloride), which is active against Plasmodium berghei in vivo (oral ID50 of 25 mu mol/kg) and multidrug-resistant Plasmodium falciparum K1 in vitro (0.17 mu M). Metaquine shows strong affinity for the putative antimalarial receptor, heme at pH 7.4 in aqueous DMSO. Both crystallographic analyses and quantum mechanical calculations (HF/6-31+G*) reveal important regions of protonation and bonding thought to persist at parasitic vacuolar pH concordant with our receptor model. Formation of drug-heme adduct in solution was confirmed using high-resolution positive ion electrospray mass spectrometry. Metaquine showed strong binding with the receptor in a 1: 1 ratio (log K = 5.7 +/- 0.1) that was predicted by molecular mechanics calculations. This study illustrates a rational multidisciplinary approach for the development of new 4-aminoquinoline antimalarials, with efficacy superior to chloroquine, based on the use of a pharmacophore model.
Resumo:
The overall and the individual rate constants of the unimolecular thermal isomerization of methylenespiropentane (4) to 1,2- and 1,3-dimethylenecyclobutanes (7 and 8) have been determined to be lg (k(-4)/s(-1)) = (13.78 +/- 0.06) - (49.7 +/- 0.2) kcal mol(-1)/RT.ln 10, lg(k(7)/s(-1)) = (13.03 +/- 0.19) - (48.0 +/- 0.6) kcal mol(-1)/RT.ln 10 and lg(k(8)/s(-1)) = (14.15 +/- 0.19) - (52.4 +/- 0.5) kcal mol(-1)/RT.ln 10, respectively. The activation energies are significantly lower than that for the rearrangement of the parent spiropentane. ((c) Wiley-VCH Verlag GmbH & Co.
Resumo:
Background: The pathogenesis of diarrhea in patients receiving enteral feeding includes colonic water secretion, antibiotic prescription, and enteropathogenic colonization, each of which involves an interaction with the gastrointestinal microbiota. Objective: The objective was to investigate temporal changes in the concentrations of fecal microbiota and short-chain fatty acids (SCFAs) in patients starting 14-d of enteral feeding and to compare these changes between patients who do and do not develop diarrhea. Design: Twenty patients starting exclusive nasogastric enteral feeding were monitored for 14 d. Fecal samples were collected at the start, middle, and end of this period and were analyzed for major bacterial groups by using culture independent fluorescence in situ hybridization and for SCFAs by using gas-liquid chromatography. Results: Although no significant changes in fecal microbiota or SCFAs were observed during enteral feeding, stark alterations occurred within individual patients. Ten patients (50%) developed diarrhea, and these patients had significantly higher concentrations of clostridia (P = 0.026) and lower concentrations (P = 0.069) and proportions (P = 0.029) of bifidobacteria. Patients with and without diarrhea had differences in the proportion of bifidobacteria (median: 0.4% and 3.7%; interquartile range: 0.8 compared with 4.3; P = 0.035) and clostridia (median: 10.4% and 3.7%; interquartile range: 14.7 compared with 7.0; P = 0.063), respectively, even at the start of enteral feeding. Patients who developed diarrhea had higher concentrations of total fecal SCFAs (P = 0.044), acetate (P = 0.029), and butyrate (P = 0.055). Conclusion: Intestinal dysbiosis occurs in patients who develop diarrhea during enteral feeding and may be involved in its pathogenesis. Am J Clin Nutr 2009; 89: 240-7.
Resumo:
A novel strain of Bifidobacterium bifidum NCIMB 41171, isolated from a faecal sample from a healthy human volunteer and able to express beta-galactosidase activity, was used in synthesis reactions for the production of galactooligosaccharide from lactose. The beta-galactosidase activity of whole bifidobacterial cells showed an optimum activity at pH 6.8-7.0 and 40 degrees C. The transgalactosylation activity of the B. bifidum cells from 50% (w/w) lactose resulted in a galactooligosaccharide mixture (20% w/w) comprising (w/w): 25% disaccharides, 35% trisaccharides, 25% tetrasaccharides and 15% pentasaccharides. Using different initial lactose concentrations, the conversion rate to galactooligosaccharides was maximum (35%) when 55% (w/w) lactose was used. In fermentation experiments, B. bifidum showed an increased preference towards the produced galactooligosaccharide mixture, displaying higher growth rate and short-chain fatty acid production when compared with commercially available oligosaccharides.
Resumo:
Background N-3 polyunsaturated fatty acids (PUFAs) from oily fish protect against death from cardiovascular disease. We aimed to assess the hypothesis that incorporation of n-3 and n-6 PUFAs into advanced atherosclerotic plaques increases and decreases plaque stability, respectively. Methods We did a randomised controlled trial of patients awaiting carotid endarterectomy. We randomly allocated patients control, sunflower oil (n-6), or fish-oil (n-3) capsules until surgery. Primary outcome was plaque morphology indicative of stability or instability, and outcome measures were concentrations of EPA, DHA, and linoleic acid in carotid plaques; plaque morphology; and presence of macrophages in plaques. Analysis was per protocol. Findings 188 patients were enrolled and randomised; 18 withdrew and eight were excluded. Duration of oil treatment was 7-189 days (median 42) and did not differ between groups. The proportions of EPA and DHA were higher in carotid plaque fractions in patients receiving fish oil compared with those receiving control (absolute difference 0.5 [95% CI 0.3-0.7], 0.4 [0.1-0.6], and 0.2 [0.1-0.4] g/100 g total fatty acids for EPA; and 0.3 [0.0-0.8], 0.4 [0.1-0.7], and 0.3 [0.1-0.6] g/100 g total fatty acids for DHA; in plaque phospholipids, cholesteryl esters, and triacylglycerols, respectively). Sunflower oil had little effect on the fatty acid composition of lipid fractions. Fewer plaques from patients being treated with fish oil had thin fibrous caps and signs of inflammation and more plaques had thick fibrous caps and no signs of inflammation, compared with plaques in patients in the control and sunflower oil groups (odds ratio 0.52 [95% CI 0.24-0.89] and 1.19 [1.02-1.57] vs control; 0.49 [0.23-0.90] and 1.16 [1.01-1.53] vs sunflower oil). The number of macrophages in plaques from patients receiving fish oil was lower than in the other two groups. Carotid plaque morphology and infiltration by macrophages did not differ between control and sunflower oil groups. Interpretation Atherosclerotic plaques readily incorporate n-3 PUFAs from fish-oil supplementation, inducing changes that can enhance stability of atherosclerotic plaques. By contrast, increased consumption of n-6 PUFAs does not affect carotid plaque fatty-acid composition or stability over the time course studied here. Stability of plaques could explain reductions in non-fatal and fatal cardiovascular events associated with increased n-3 PUFA intake.
Resumo:
The aim was to investigate (i) the occurrence of sublethal injury in Listeria monocytogenes, Escherichia coli, and Saccharomyces cerevisiae after high hydrostatic pressure (HHP) treatment as a function of the treatment medium pH and composition and (ii) the relationship between the occurrence of sublethal injury and the inactivating effect of a combination of HHP and two antimicrobial compounds, tert-butyl hydroquinone (TBHQ) and citral. The three microorganisms showed a high proportion of sublethally injured cells (up to 99.99% of the surviving population) after HHP. In E. coli and L. monocytogenes, the extent of inactivation and sublethal injury depended on the pH and the composition of the treatment medium, whereas in S. cerevisiae, inactivation and sublethal injury were independent of medium pH or composition under the conditions tested. TBHQ alone was not lethal to E. coli or L. monocytogenes but acted synergistically with HHP and 24-h refrigeration, resulting in a viability decrease of >5 log(10) cycles of both organisms. The antimicrobial effect of citral depended on the microorganism and the treatment medium pH. Acting alone for 24 h under refrigeration, 1,000 ppm of citral caused a reduction of 5 log(10) cycles of E. coli at pH 7.0 and almost 3 log(10) cycles of L. monocytogenes at pH 4.0. The combination of citral and HHP also showed a synergistic effect. Our results have confirmed that the detection of sublethal injury after HHP may contribute to the identification of those treatment conditions under which HHP may act synergistically with other preserving processes.