947 resultados para High selectivity
Resumo:
This study examines the selectivity and timing performance of 218 UK investment trusts over the period July 1981 to June 2009. We estimate the Treynor and Mazuy (1966) and Henriksson and Merton (1981) models augmented with the size, value, and momentum factors, either under the OLS method adjusted with the Newey-West procedure or under the GARCH(1,1)-in-mean method following the specification of Glosten et al. (1993; hereafter GJR-GARCH-M). We find that the OLS method provides little evidence in favour of the selectivity and timing ability, consistent with previous studies. Interestingly, the GJR-GARCH-M method reverses this result, showing some relatively strong evidence on favourable selectivity ability, particularly for international funds, as well as favourable timing ability, particularly for domestic funds. We conclude that the GJR-GARCH-M method performs better in evaluating fund performance compared with the OLS method and the non-parametric approach, as it essentially accounts for the time-varying characteristics of factor loadings and hence obtains more reliable results, in particular, when the high frequency data, such as the daily returns, are used in the analysis. Our results are robust to various in-sample and out-of-sample tests and have valuable implications for practitioners in making their asset allocation decisions across different fund styles. © 2012 Elsevier B.V.
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Ultrathin alumina monolayers grafted onto an ordered mesoporous SBA-15 silica framework afford a composite catalyst support with unique structural properties and surface chemistry. Palladium nanoparticles deposited onto Al-SBA-15 via wet impregnation exhibit the high dispersion and surface oxidation characteristic of pure aluminas, in conjunction with the high active site densities characteristic of thermally stable, high-area mesoporous silicas. This combination confers significant rate enhancements in the aerobic selective oxidation (selox) of cinnamyl alcohol over Pd/Al-SBA-15 compared to mesoporous alumina or silica supports. Operando, liquid-phase XAS highlights the interplay between dissolved oxygen and the oxidation state of palladium nanoparticles dispersed over Al-SBA-15 towards on-stream reduction: ambient pressures of flowing oxygen are sufficient to hinder palladium oxide reduction to metal, enabling a high selox activity to be maintained, whereas rapid PdO reduction and concomitant catalyst deactivation occurs under static oxygen. Selectivity to the desired cinnamaldehyde product mirrors these trends in activity, with flowing oxygen minimising CO cleavage of the cinnamyl alcohol reactant to trans-β-methylstyrene, and of cinnamaldehyde decarbonylation to styrene. © 2013 Elsevier B.V.
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Chemoselectivity is a cornerstone of catalysis, permitting the targeted modification of specific functional groups within complex starting materials. Here we elucidate key structural and electronic factors controlling the liquid phase hydrogenation of cinnamaldehyde and related benzylic aldehydes over Pt nanoparticles. Mechanistic insight from kinetic mapping reveals cinnamaldehyde hydrogenation is structure-insensitive over metallic platinum, proceeding with a common Turnover Frequency independent of precursor, particle size or support architecture. In contrast, selectivity to the desired cinnamyl alcohol product is highly structure sensitive, with large nanoparticles and high hydrogen pressures favoring C=O over C=C hydrogenation, attributed to molecular surface crowding and suppression of sterically-demanding adsorption modes. In situ vibrational spectroscopies highlight the role of support polarity in enhancing C=O hydrogenation (through cinnamaldehyde reorientation), a general phenomenon extending to alkyl-substituted benzaldehydes. Tuning nanoparticle size and support polarity affords a flexible means to control the chemoselective hydrogenation of aromatic aldehydes.
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The ability to tune the structural and chemical properties of colloidal nanoparticles (NPs), make them highly advantageous for studying activity and selectivity dependent catalytic behaviour. Incorporating pre-synthesized colloidal NPs into porous supports materials remains a challenge due to poor wetting and pore permeability. In this report monodisperse, composition controlled AgPd alloy NPs were synthesised and embedded into SBA-15 using supercritical carbon dioxide and hexane. Supercritical fluid impregnation resulted in high metal loading without the requirement for surface pre-treatments. The catalytic activity, reaction profiles and recyclability of the alloy NPs embedded in SBA-15 and immobilised on non-porous SiO2 are evaluated. The NPs incorporated within the SBA-15 porous network showed significantly greater recyclability performance compared to non-porous SiO2.
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Cold-water corals form prominent reef ecosystems along ocean margins that depend on suspended resources produced in surface waters. In this study, we investigated food processing of 13C and 15N labelled bacteria and algae by the cold-water coral Lophelia pertusa. Coral respiration, tissue incorporation of C and N and metabolic-derived C incorporation into the skeleton were traced following the additions of different food concentrations (100, 300, 1300 µg C/l) and two ratios of suspended bacterial and algal biomass (1:1, 3:1). Respiration and tissue incorporation by L. pertusa increased markedly following exposure to higher food concentrations. The net growth efficiency of L. pertusa was low (0.08±0.03), which is consistent with their slow growth rates. The contribution of algae and bacteria to total coral assimilation was proportional to the food mixture in the two lowest food concentrations, but algae were preferred over bacteria as food source at the highest food concentration. Similarly, the stoichiometric uptake of C and N was coupled in the low and medium food treatment, but was uncoupled in the high food treatment and indicated a comparatively higher uptake or retention of bacterial carbon as compared to algal nitrogen. We argue that behavioural responses for these small-sized food particles, such as tentacle behaviour, mucus trapping and physiological processing, are more likely to explain the observed food selectivity as compared to physical-mechanical considerations. A comparison of the experimental food conditions to natural organic carbon concentrations above CWC reefs suggests that L. pertusa is well adapted to exploit temporal pulses of high organic matter concentrations in the bottom water caused by internal waves and down-welling events.
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Catch effort data on which fisheries management regulations are sometimes based are not available for most lakes in Uganda. However, failure to regulate fishing gears and methods has been a major cause of collapse of fisheries in the country. Fisheries have been damaged by destructive and non-selective fishing gears and methods such as trawling and beach seining, by use of gill nets of mesh size which crop immature fish and by introduction of mechanised fishing. Selectivity of gears used to crop Lates niloticus L.(Nile perch), Oreochromis niloticus L. (Nile tilapia) and Rastrineobola argentea Pellegrin (Mukene) which are currently the most important commercial species in Uganda were examined in order to recommend the most suitable types, sizes and methods that should be used in exploiting these fisheries. Gill nets of less than 127 mm mainly cropped immature Nile tilapia and Nile perch. To protect these fisheries, the minimum mesh size of gill nets should be set at 127 mm. Seine nets of 5 mm caught high proportions in immature Mukene while those of 10 mm caught mainly mature Mukene. When operated inshore, both sizes caught immature Nile perch and Nile tilapia as by-catch. To protect the Mukene fishery and avoid catching immature bye-catch, a minimum mesh size of the Mukene net should be 10 mm operated as Lampara type net offshore, but since most fishermen have been using 5 mm seine nets for over five years the minimum size should not be allowed to drop below 5 mm pending further thorough investigations. Beach seining and trawling are destructive to fisheries and should be prohibited until data that may justify their use is available.
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Aiming to introduce a multiresidue analysis for the trace detection of pesticide residues belonging to organophosphorus and triazine classes from olive oil samples, a new sample preparation methodology comprising the use of a dual layer of “tailor-made” molecularly imprinted polymers (MIPs) SPE for the simultaneous extraction of both pesticides in a single procedure has been attempted. This work has focused on the implementation of a dual MIP-layer SPE procedure (DL-MISPE) encompassing the use of two MIP layers as specific sorbents. In order to achieve higher recovery rates, the amount of MIP layers has been optimized as well as the influence of MIP packaging order. The optimized DL-MISPE approach has been used in the preconcentration of spiked organic olive oil samples with concentrations of dimethoate and terbuthylazine similar to the maximum residue limits and further quantification by HPLC. High recovery rates for dimethoate (95%) and terbuthylazine (94%) have been achieved with good accuracy and precision. Overall, this work constitutes the first attempt on the development of a dual pesticide residue methodology for the trace analysis of pesticide residues based on molecular imprinting technology. Thus, DL-MISPE constitutes a reliable, robust, and sensitive sample preparation methodology that enables preconcentration of the target pesticides in complex olive oil samples, even at levels similar to the maximum residue limits enforced by the legislation.
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Proline (Pro) is a unique amino acid that has been examined previously as a potential chiral selector for high-performance liquid chromatography. In recent years, a new class of promising Pro based enantioselective stationary phases has been studied and the longer peptides were found to be competitive with commercial chiral stationary phases (CSPs). Here, we aim to perform a comprehensive examination of a t-butoxycarbonyl- (t-Boc-) terminated monoproline selector. This selector was grafted through an amide linkage to an aminopropyl siloxane-terminated Si (111) wafer and to a silicon atomic force microscopy tip. To ensure a flat, homogeneous overlayer of selectors suitable for force spectrometric measurements, the prepared surfaces were characterized using XPS, AFM and contact angle measurements. Chemical force spectrometry (CFS) has been used to examine the chiral discrimination in our monoproline CSP by measuring the interaction forces between two D- or L-monoproline monolayers in water and in the presence of a series of amino acids in solution to explore the degree to which binding of amino acids impacts self-selectivity. Chemical force titration (CFT) has been used to observe the influence of variations in pH on the binding interaction of proline modified chiral surfaces. Here we aim to explore the connection between side-chain hydrophobicity and differences in the nature of the binding between different ionic forms of amino acids and the t-Boc-Pro interface, and thereby to gain insight into the mechanism of chiral selectivity. The CFS results show several trends for different proline selector/amino acid combinations and indicate that the binding characteristics of amino acid to the proline surface is strongly dependent on the amino acid side chain where hydrophilic side chain amino acids exhibit a selectivity opposite to that seen for those with hydrophobic side chains. The CFT studies also provide valuable insights into interactions between the proline selector and the amino acids under a wide range of pH conditions, indicating that protonated amine groups of alanine and serine are closely involved in the binding mechanism to proline surfaces. On the other hand, the presence of the second carboxylic group in aspartic acid plays an important role while interacting with proline.
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A study of European hake Merluccius merluccius gill net selectivity was undertaken off the Algarve (Southern Portugal), between 1999 and 2001. Four nominal mesh sizes (70, 80, 90 and 100 mm) were used in fishing trials and the 'share each length class catch total' (SELECT) method was used to fit gill net selectivity curves. Hake were caught in the same size range by all mesh sizes, between 17 and 65 cm total length. While most fishes were wedged, significant and similar proportions were entangled in all mesh sizes, contributing to the wide size range, and in some cases, bimodal shape of catch size frequency distributions. Insignificant numbers of undersized hake were caught, with most catches consisting of mature female fish. Catch rates decreased sharply with increasing mesh size. The bimodal model gave the best fit for hake that were wedged, with estimated modal lengths of 40.1, 46.7 and 51.0 cm for the 70, 80 and 90 mm nominal mesh sizes, respectively. The high catch per unit effort of the smallest mesh size, with most fish caught being female, together with the fact that the modal length of the fitted selectivity curve is well below the size at maturity for hake in Portuguese waters, suggests that the 80 mm nominal mesh size is more appropriate for ensuring resource sustainability.
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A longline 'metier' using small hooks for 'red' sea breams (Pagellus acarne and Pagellus erythrinus) in the Algarve (south of Portugal) was studied. Experimental longlining was carried out with three sizes of "Mustad" round bend, flatted, spade end Quality 2316 DT hooks (numbers 11, 13 and 15) and two types of bait: razor shell (Ensis siliqua) and mud shrimp (Upogebia pusilla). A total of 3 328 fish and at least 36 species were caught with 33 600 hooks fished in 28 longline sets. Five species of sea breams (Sparidae) accounted for 79% of the catch: Pagellus acarne, Pagellus erythrinus, Diplodus vulgaris, Spondyliosoma cantharus, and Boops boops. High catch rates of 20-30 fish per 100 hooks were made in a number of 1 200 hook longline sets, with total catch weights of 40 to more than 60 kg per set. In general, the smallest hook (number 15) had the highest catch rate. Bait type did not significantly affect the catch size distributions. Although more fish were caught with the razor shell bait, higher catch rates of 'red' sea breams were obtained with mud shrimp. Catch rates were also affected by the location of the fishing grounds and the time of the set, with the highest catch rates obtained when the longline was set within two hours before sunrise. A wide size range was caught for each species, with highly overlapped catch size frequency distributions for the three hook sizes used. Except for Spondyliosoma cantharus, few illegal-sized fish were caught, even with the smallest hook. The logistic model fitted by maximum likelihood was used to describe hook selectivity for Diplodus vulgaris, Pagellus acarne, Pagellus erythrinus, and Spondyliosoma cantharus. (C) Ifremer-Elsevier, Paris.
Resumo:
Three long-line methods have been studied in the Algarve: 1) small-hook long-line for inshore (less than 30 m) ‘white’ sea breams (Sparidae); 2) small-hook long-line for deeper water (40-60 m) ‘red’ sea breams; and 3) deep water (500-700 m) semi-pelagic long-line for hake Merluccius merluccius (Linnaeus, 1758). Selectivity studies were carried out with three hook sizes in the first two cases: Mustad round-bent Quality 2369 hooks, numbers 15, 13, and 11, baited with a standardsized razor-shell Ensis siliqua (Linnaeus, 1758). Four hook sizes (numbers 10, 9, 7, and 5) of Stell round-bent, eyed hooks were used in the semi-pelagic long-line selectivity study, baited with a half of a standard-sized sardine. Some factors affecting catch composition and catch rates of the small hook long-lines were also evaluated: bait, gangion length, setting time, fishing ground, and depth. Species diversity was relatively high, with 40, 36 and 27 species, respectively, in the three studies. However, the catches were dominated by a limited number of species. Catch rates (number of fish per 100 hooks) were variable (< 5 %; > 20 %), with a general decrease in catch rate with increasing hook size in all the studies. In general, the catch size distributions for the different hook sizes for each species were highly overlapping, with little or no evidence of differences in size selectivity. Hooks caught a wide size-range for each species, with few or no illegal-sized fish, in most cases. Some implications of these results for the management of multi-species, multi-gear fisheries are discussed.
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The thermal decomposition of natural ammonium oxalate known as oxammite has been studied using a combination of high resolution thermogravimetry coupled to an evolved gas mass spectrometer and Raman spectroscopy coupled to a thermal stage. Three mass loss steps were found at 57, 175 and 188°C attributed to dehydration, ammonia evolution and carbon dioxide evolution respectively. Raman spectroscopy shows two bands at 3235 and 3030 cm-1 attributed to the OH stretching vibrations and three bands at 2995, 2900 and 2879 cm-1, attributed to the NH vibrational modes. The thermal degradation of oxammite may be followed by the loss of intensity of these bands. No intensity remains in the OH stretching bands at 100°C and the NH stretching bands show no intensity at 200°C. Multiple CO symmetric stretching bands are observed at 1473, 1454, 1447 and 1431cm-1, suggesting that the mineral oxammite is composed of a mixture of chemicals including ammonium oxalate dihydrate, ammonium oxalate monohydrate and anhydrous ammonium oxalate.