200 resultados para lengthening


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The solution conformations of the -hybrid oligopeptides Boc-Aib-4(R)Val]n-OMe (n = 1-8) in organic solvents have been probed by NMR, IR, and CD spectroscopic methods. In the solid state, this peptide series favors C12-helical conformations, which are backbone-expanded analogues of 310 helices in -peptide sequences. NMR studies of the six- (n = 3) and 16-residue (n = 8) peptides reveal that only two NH protons attached the N-terminus residues Aib(1) and 4(R)Val(2) are solvent-exposed. Sequential NiH-Ni+1H NOEs characteristic of local helical conformations are also observed at the residues. IR studies establish that chain extension leads to a large enhancement in the intensities of the hydrogen-bonded NH stretching bands (3343-3280 cm-1), which suggest elongation of intramolecularly hydrogen-bonded structures. The development of C12-helical structures upon lengthening of the sequence is supported by the NMR and IR observations. The CD spectra of the ()n peptides reveal a negative maximum at ca. 206 nm and a positive maximum at ca. 192 nm, spectral feature that are distinct from those of 310 helices in -peptides.

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In this paper, we report the gas phase infrared spectra of fluorene and its methylated derivatives using a heated multipass cell and argon as a carrier gas. The observed spectra in the 4000-400 cm(-1) range have been fitted using the modified scaled quantum mechanical force field (SQMFF) calculation with the 6-311G** basis. The advantage of using the modified SQMFF method is that it scales the force constants to find the best fit to the observed spectral lines by minimizing the fitting error. In this way we are able to assign all the observed fundamental bands in the spectra. With consecutive methyl substitutions two sets of bands are found to shift in a systematic way. The set of four aromatic C-H stretching vibrations around 3000 cm(-1) shifts toward lower frequencies while the single most intense aromatic C-H out-of-plane bending mode around 750 cm(-1) shifts toward higher frequencies. The reason for shifting of aromatic C-H stretching frequency toward lower wave numbers with gradual methyl substitution has been attributed to the lengthening of the C-H bonds due to the +I effect of the methyl groups to the ring current as revealed from the calculations. While the unexpected shifting of the aromatic C-H out-of-plane bend toward higher wave numbers with increasing methyl substitution is ascribed to the lowering of the number of adjacent aromatic C-H bonds on the plane of the benzene ring with gradual methyl substitutions. (C) 2013 Elsevier B.V. All rights reserved.

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Executive Summary: Observations show that warming of the climate is unequivocal. The global warming observed over the past 50 years is due primarily to human-induced emissions of heat-trapping gases. These emissions come mainly from the burning of fossil fuels (coal, oil, and gas), with important contributions from the clearing of forests, agricultural practices, and other activities. Warming over this century is projected to be considerably greater than over the last century. The global average temperature since 1900 has risen by about 1.5ºF. By 2100, it is projected to rise another 2 to 11.5ºF. The U.S. average temperature has risen by a comparable amount and is very likely to rise more than the global average over this century, with some variation from place to place. Several factors will determine future temperature increases. Increases at the lower end of this range are more likely if global heat-trapping gas emissions are cut substantially. If emissions continue to rise at or near current rates, temperature increases are more likely to be near the upper end of the range. Volcanic eruptions or other natural variations could temporarily counteract some of the human-induced warming, slowing the rise in global temperature, but these effects would only last a few years. Reducing emissions of carbon dioxide would lessen warming over this century and beyond. Sizable early cuts in emissions would significantly reduce the pace and the overall amount of climate change. Earlier cuts in emissions would have a greater effect in reducing climate change than comparable reductions made later. In addition, reducing emissions of some shorter-lived heat-trapping gases, such as methane, and some types of particles, such as soot, would begin to reduce warming within weeks to decades. Climate-related changes have already been observed globally and in the United States. These include increases in air and water temperatures, reduced frost days, increased frequency and intensity of heavy downpours, a rise in sea level, and reduced snow cover, glaciers, permafrost, and sea ice. A longer ice-free period on lakes and rivers, lengthening of the growing season, and increased water vapor in the atmosphere have also been observed. Over the past 30 years, temperatures have risen faster in winter than in any other season, with average winter temperatures in the Midwest and northern Great Plains increasing more than 7ºF. Some of the changes have been faster than previous assessments had suggested. These climate-related changes are expected to continue while new ones develop. Likely future changes for the United States and surrounding coastal waters include more intense hurricanes with related increases in wind, rain, and storm surges (but not necessarily an increase in the number of these storms that make landfall), as well as drier conditions in the Southwest and Caribbean. These changes will affect human health, water supply, agriculture, coastal areas, and many other aspects of society and the natural environment. This report synthesizes information from a wide variety of scientific assessments (see page 7) and recently published research to summarize what is known about the observed and projected consequences of climate change on the United States. It combines analysis of impacts on various sectors such as energy, water, and transportation at the national level with an assessment of key impacts on specific regions of the United States. For example, sea-level rise will increase risks of erosion, storm surge damage, and flooding for coastal communities, especially in the Southeast and parts of Alaska. Reduced snowpack and earlier snow melt will alter the timing and amount of water supplies, posing significant challenges for water resource management in the West. (PDF contains 196 pages)

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[ES] La posibilidad de contar como larga una sílaba breve acabada en consonante y ante cesura es una licencia que, aunque utilizada parcamente por todos los poetas latinos de la Antigüedad, siempre ha sido reconocida como tal. No ocurre lo mismo con los casos de alargamiento en sílaba abierta: rodeados de problemas de diverso tipo, han sido vistos con frecuencia como un fenómeno distinto del anterior. A partir de los testimonios de algunos gramáticos antiguos, se postula la existencia de una estricta prohibición de tales alargamientos de sílabas abiertas a partir de mediados del siglo I d.C.

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Channeling by a train of laser pulses into homogeneous and inhomogeneous plasmas is studied using particle-in-cell simulation. When the pulse duration and the interval between the successive pulses are appropriate, the laser pulse train can channel into the plasma deeper than a single long-pulse laser of similar peak intensity and total energy. The increased penetration distance can be attributed to the repeated actions of the ponderomotive force, the continuous between-pulse channel lengthening by the inertially evacuating ions, and the suppression of laser-driven plasma instabilities by the intermittent laser-energy cut-offs.

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Several new ligand platforms designed to support iron dinitrogen chemistry have been developed. First, we report Fe complexes of a tris(phosphino)alkyl (CPiPr3) ligand featuring an axial carbon donor intended to conceptually model the interstitial carbide atom of the nitrogenase iron-molybdenum cofactor (FeMoco). It is established that in this scaffold, the iron center binds dinitrogen trans to the Calkyl anchor in three structurally characterized oxidation states. Fe-Calkyl lengthening is observed upon reduction, reflective of significant ionic character in the Fe-Calkyl interaction. The anionic (CPiPr3)FeN2- species can be functionalized by a silyl electrophile to generate (CPiPr3)Fe-N2SiR3. This species also functions as a modest catalyst for the reduction of N2 to NH3. Next, we introduce a new binucleating ligand scaffold that supports an Fe(μ-SAr)Fe diiron subunit that coordinates dinitrogen (N2-Fe(μ-SAr)Fe-N2) across at least three oxidation states (FeIIFeII, FeIIFeI, and FeIFeI). Despite the sulfur-rich coordination environment of iron in FeMoco, synthetic examples of transition metal model complexes that bind N2 and also feature sulfur donor ligands remain scarce; these complexes thus represent an unusual series of low-valent diiron complexes featuring thiolate and dinitrogen ligands. The (N2-Fe(μ-SAr)Fe-N2) system undergoes reduction of the bound N2 to produce NH3 (~50% yield) and can efficiently catalyze the disproportionation of N2H4 to NH3 and N2. The present scaffold also supports dinitrogen binding concomitant with hydride as a co-ligand. Next, inspired by the importance of secondary-sphere interactions in many metalloenzymes, we present complexes of iron in two new ligand scaffolds ([SiPNMe3] and [SiPiPr2PNMe]) that incorporate hydrogen-bond acceptors (tertiary amines) which engage in interactions with nitrogenous substrates bound to the iron center (NH3 and N2H4). Cation binding is also facilitated in anionic Fe(0)-N2 complexes. While Fe-N2 complexes of a related ligand ([SiPiPr3]) lacking hydrogen-bond acceptors produce a substantial amount of ammonia when treated with acid and reductant, the presence of the pendant amines instead facilitates the formation of metal hydride species.

Additionally, we present the development and mechanistic study of copper-mediated and copper-catalyzed photoinduced C-N bond forming reactions. Irradiation of a copper-amido complex, ((m-tol)3P)2Cu(carbazolide), in the presence of aryl halides furnishes N-phenylcarbazole under mild conditions. The mechanism likely proceeds via single-electron transfer from an excited state of the copper complex to the aryl halide, generating an aryl radical. An array of experimental data are consistent with a radical intermediate, including a cyclization/stereochemical investigation and a reactivity study, providing the first substantial experimental support for the viability of a radical pathway for Ullmann C-N bond formation. The copper complex can also be used as a precatalyst for Ullmann C-N couplings. We also disclose further study of catalytic Calkyl-N couplings using a CuI precatalyst, and discuss the likely role of [Cu(carbazolide)2]- and [Cu(carbazolide)3]- species as intermediates in these reactions.

Finally, we report a series of four-coordinate, pseudotetrahedral P3FeII-X complexes supported by tris(phosphine)borate ([PhBP3FeR]-) and phosphiniminato X-type ligands (-N=PR'3) that in combination tune the spin-crossover behavior of the system. Low-coordinate transition metal complexes such as these that undergo reversible spin-crossover remain rare, and the spin equilibria of these systems have been studied in detail by a suite of spectroscopic techniques.

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Esta dissertação tem como objetivo analisar a trajetória escolar de jovens de origem popular e oriundos de um bairro de periferia da cidade do Rio de Janeiro, que ingressaram em cursos de pós-graduação stricto sensu de importantes universidades públicas. Tais trajetórias serão aqui analisadas a partir das narrativas dos próprios atores sociais em questão, buscando evidenciar as marcas de sua socialização e formação escolar em um contexto social que, do ponto de vista de algumas análises no campo da sociologia da educação, não favoreceriam a aquisição do capital cultural e social necessários ao ingresso na carreira acadêmica. Desta perspectiva, além de não serem muito comuns nos meios populares, essas trajetórias também não seriam reconhecidas pelo grupo de origem que, na maioria das vezes, identifica a formação escolar como porta de entrada no mundo do trabalho, tendo no curso superior o ponto máximo de uma formação escolar bem sucedida. Busca-se aqui, a partir da análise do conjunto dessas trajetórias, apreender os elementos e experiências sociais que possibilitaram esse prolongamento na formação escolar, e, sobretudo, o impacto e o significado da inserção na carreira acadêmica, tanto do ponto de vista da mobilidade social quanto dos conflitos decorrentes dessa experiência subjetiva, quer em relação às expectativas familiares ou do grupo social de origem. O trabalho de campo de caráter etnográfico, baseado na observação participante e realização de entrevistas aprofundadas constituíram as ferramentas metodológicas básicas a partir das quais essa pesquisa foi desenvolvida. Com relação à discussão teórica aqui proposta tomou-se como referência os trabalhos de Pierre Bourdieu, Jean-Claude Passeron, Bernard Lahire, Jailson de Souza e Silva e Maria da Graça Jacintho Setton, entre outros

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Several insectivorous bats have included fish in their diet, yet little is known about the processes underlying this trophic shift. We performed three field experiments with wild fishing bats to address how they manage to discern fish from insects and adapt their hunting technique to capture fish. We show that bats react only to targets protruding above the water and discern fish from insects based on prey disappearance patterns. Stationary fish trigger short and shallow dips and a terminal echolocation pattern with an important component of the narrowband and low frequency calls. When the fish disappears during the attack process, bats regulate their attack increasing the number of broadband and high frequency calls in the last phase of the echolocation as well as by lengthening and deepening their dips. These adjustments may allow bats to obtain more valuable sensorial information and to perform dips adjusted to the level of uncertainty on the location of the submerged prey. The observed ultrafast regulation may be essential for enabling fishing to become cost-effective in bats, and demonstrates the ability of bats to rapidly modify and synchronise their sensorial and motor features as a response to last minute stimulus variations.

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A cicatrização constitui processo complexo envolvendo diferentes sistemas biológicos e imunológicos , sendo essencial para manter a integridade do organismo. Três fases bem definidas ocorrem, a inflamatória, a proliferativa e a de maturação. A falha ou prolongamento em uma fase pode resultar em retardo da cicatrização tecidual. A sutura dos tecidos e sua cicatrização é um dos fundamentos básicos da cirurgia e a procura de substâncias que melhorem este processo é um desafio constante. O uso de substâncias de plantas têm sido testados por vários autores. Objetivo - Analisar comparativamente as alterações macroscópicas e histológicas proporcionadas pelo uso do extrato bruto da Jatropha gossypiifolia intraperitonial, na cicatrização de suturas realizadas na bexiga urinária de ratos. Material e método Sessenta ratos da linhagem Wistar, adultos, machos foram distribuídos em 2 grupos animais. O procedimento experimental constituiu-se em laparotomia mediana infraumbelical, incisão longitudinal de 1cm na parede ventral da bexiga e síntese em plano único com pontos separados de poliglactina 910 5-0 (Ethicon). O procedimento nos animais do grupo controle (ratos 1 a 30) instilou-se na cavidade peritonial água destilada na proporção de 1ml por kg de peso e no grupo Jatropha (ratos 31 a 60) utiilizou-se o extrato bruto de Jatropha gossypiifolia na proporção de 1ml por kg de peso, que representava 200mg do fototerápico, intraperitoneal. Cada grupo foi dividido em 3 subgrupos de 10 animais sendo estes submetidos à eutanásia no 7 e 14 pós-operatório. Foi feita análise macroscópica e histológica comparativa entre os subgrupos . Resultados - No 7 dia foi observado diferença estatisticamente significativa nas variáveis inflamação aguda, neoformação vascular e colagenização, sendo a primeira maior no grupo controle e as duas últimas no grupo Jatropha; no 14 variáveis inflamação aguda e proliferação fibroblástica apresentaram-se mais intensas com significado estatístico no grupo controle. No 21 dia as variantes se alinharam não havendo diferença estatística na sua comparação. Conclusão - Foi observado homogeneidade na cicatrização nos 2 grupos, contudo, a mesma foi mais intensa no grupo controle. Não se observou, portanto, efeito favorecedor cicatrizante do extrato bruto da Jatropha gossypiifolia intraperitonial, em dose única, na bexiga urinária de rato.

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O crescimento da população e dos núcleos urbanos durante o século XX, sobretudo nos países em desenvolvimento, contribuiu para o aumento das áreas impermeáveis das bacias hidrográficas, com impactos importantes nos sistemas de drenagem urbana e na ocorrência de enchentes associadas. As enchentes trazem prejuízos materiais, na saúde e sociais. Recentemente, têm sido propostas práticas conservacionistas e medidas compensatórias, que buscam contribuir para o controle das enchentes urbanas, através do retardo do pico e amortecimento dos hidrogramas. Modelos matemáticos hidrológicos-hidráulicos permitem a simulação da adoção destas medidas de controle, demonstrando e otimizando sua localização. Esta dissertação apresenta os resultados da aplicação do modelo hidrológico Storm Water Management Model (SWMM) à bacia hidrográfica de estudo e representativa do rio Morto localizada em área peri-urbana em Jacarepaguá na cidade do Rio de Janeiro, com área de 9,41 km. O processamento do modelo SWMM foi realizado com o apoio da interface Storm and Sanitary Analysis (SSA), integrada ao sistema AutoCAD Civil 3D. Além da verificação da adequabilidade do modelo à representação dos sistemas hidrológico e hidráulico na bacia, foram desenvolvidos estudos para dois cenários como medidas de controle de enchentes: cenário 1, envolvendo implantação de um reservatório de detenção e, cenário 2, considerando a implantação de reservatórios de águas pluviais nos lotes. Os hidrogramas resultantes foram comparados ao hidrograma resultante da simulação nas condições atuais. Além disso, foram avaliados os custos associados a cada um dos cenários usando o sistema de orçamento da Empresa Rio Águas da PCRJ. Nas simulações foram adotadas a base cartográfica, e os dados climatológicos e hidrológicos previamente observados no contexto do projeto HIDROCIDADES, Rede de Pesquisa BRUM/FINEP, na qual este estudo se insere. Foram representados os processos de geração e propagação do escoamento superficial e de base. Durante o processo de calibração, realizou-se a análise de sensibilidade dos parâmetros, resultando como parâmetros mais sensíveis os relativos às áreas impermeáveis, especialmente o percentual de área impermeável da bacia (Ai). A calibração foi realizada através do ajuste manual de sete parâmetros do escoamento superficial e cinco do escoamento de base para três eventos. Foram obtidos coeficientes de determinação entre 0,52 e 0,64, e a diferença entre os volumes escoados e observados entre 0,60% e 4,96%. Para a validação do modelo foi adotado um evento pluviométrico excepcional observado na cidade em abril de 2010, que à época causou enchentes e grandes transtornos na cidade. Neste caso, o coeficiente de determinação foi igual a 0,78 e a diferença entre volumes foi de 15%. As principais distorções entre hidrogramas observados e simulados foram verificados para as vazões máximas. Em ambos os cenários as enchentes foram controladas. A partir destes estudos, pôde-se concluir que o melhor custo-benefício foi o cenário 2. Para este cenário, foi observado maiores amortecimento e retardo da vazão de pico do hidrograma, igual a 21,51% da vazão simulada para as condições atuais da bacia. Os custos de implantação orçados para os reservatórios de lote ficaram 52% a menos do que o do reservatório de detenção.

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The use of catenary steel-compliant-riser (SCR) systems has increased as hydrocarbon production has moved progressively farther offshore and into deeper waters. The issue of fatigue damage caused by cyclic interaction of a riser with the seabed has gained prominence with the widespread use of SCRs and with the lengthening of the spans. The problem involves a number of complex factors, including trench configuration, nonlinear soil stiffness, breakaway of the riser from the seafloor, and degradation of soil resistance during cyclic loading. This paper presents a soilinteraction model capable of modeling these complexities, using input parameters that can be obtained with reasonable expenditure. Model simulations for typical offshore soft-soil conditions indicate that the model is capable of realistic predictions of cyclic bending moments. The degradation of soil resistance has a major effect on cyclic bending moments, particularly when uplift motions at the riser touchdown point (TDP) are large. © 2008 Society of Petroleum Engineers.

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A laboratory-based methodology to launch cylindrical sand slugs at high velocities is developed. The methodology generates well-characterised soil ejecta without the need for detonation of an explosive; this laboratory-based tool thereby allows for the experimental investigation of the soil-structure events. The experimental set-up comprises a launcher with a cylindrical cavity and a piston to push out the sand slug. The apparatus is used to launch both dry and water-saturated sand slugs. High speed photography is used to characterise the evolution of the sand slugs after launch. We find that the diameter of the slugs remains unchanged, and the sand particles possess only an axial component of velocity. However, the sand particles have a uniform spatial gradient of axial velocity and this results in lengthening of the slugs as they travel towards their target. Thus, the density of the sand slugs remains spatially homogenous but decreases with increasing time. The velocity gradient is typically higher in the dry sand slugs than that of the water-saturated slugs. The pressure exerted by the slugs on a rigid-stationary target is measured by impacting the slugs against a direct impact Kolsky bar. After an initial high transient pressure, the pressure reduces to a value of approximately ρv 2 where ρ is the density of the impacting sand slug and v is the particle velocity. This indicates that loading due to the sand is primarily inertial in nature. The momentum transmitted to the Kolsky bar was approximately equal to the incident momentum of the sand slugs, regardless of whether they are dry or water-saturated. © 2013 Elsevier Ltd. All rights reserved.

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This research, mainly by using perceptual experiment and relating its results to the acoustic correlates, investigated the acoustic correlates of mandarin prominences of prosodic word、prosodic phrase、sentence and their mutual influences. The results are as follow: (1) for the prominence of prosodic word, according the order of the extents to which these acoustic correlates contribute to the perception of the prominence, its acoustic correlates are duration、pitch、spectral tilt、energy and pitch-change, the results also have showed that the perception of the prominence is influenced by some non-acoustic factors; (2) for the prominence of prosodic phrase, baseing on the experimental results, the existing of prosodic phrase prominence in mandarian has been proposed, and the experiments proved that the prosodic phrase prominence fall on the semantic focus of the phrase typically; (3) for the prominence of sentence, the experimental results show that, the lengthening of duration, similar with the pitch-change, mainly localised on the prosodic head of the domain on which the sentence prominence emphisize, and this lengthening would, in different levels, spread on other syllables in the phonetic constituents which contain the prosodic head, and this pattern of lengthening of duration does not vary with changing of domain of sentence prominence, that means, in mandarin sentence, there is generally no acoustic cues which can been used in the perception of the domain of sentnece prominence; (4) for the acoustic cues of mutual influences of the prominences of different levels, the experiment have proved that, not only the pitch-change but also the lengthening of duration are subjective to melodic grid law. In the last part of the dissertation, I have tried to given an explantion about the above experimental results from psylogical view point.

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This schematic geological cross-section of Angola offshore is representative of the majority of the Atlantic-type divergent margins. It illustrates the main geological features allowing to understand the different petroleum systems occurring, particularly, in South Atlantic divergent margins : (i) Pre-Pangea rocks (Precambrian granite-gneiss basement, volcanic rocks an/ or Paleozoic sediments, more or less, metamorphosed), which lie underneath the pre-rifting unconformity (PRU), in blue in the cross-section ; (ii) The rift-type basins developed during the lengthening of the Pangea supercontinent ; (iii) The breakup unconformity (BUU), which highlight the upper limit of the rift-type basins, in which organic rich lacustrine shales with a parallel internal configuration are potential source-rocks (organic matter type I) ; (iv) The SDRs (seaward dipping reflectors), which, generally, do not have any generating hydrocarbon potential (just 5 m of lacustrine shales are known in Austral basin) ; (v) The BUU is fossilized by SDRs (subaerial volcanism) or by margin infra-salt sediments (forming the mistakenly called by some American geoscientists "sag basin") ; (vi) The Loeme salt basin, which is a twin of the Brazilian salt basin, that is to say, that both basins have always been individualized ; (vii) The transgressive (backstepping) and regressive (forestepping) phases of the post-Pangea continental encroachment cycle ; (v) The interface between these sedimentary phases, correspond to the emplacement of potential marine source-rocks (organic matter type-II) ; (vi) Potential dispersive source rocks (organic matter type III) are possible in the regressive sedimentary interval.

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The social dimensions of marine protected areas (MPAs) play an important role in MPA success, yet these social dimensions are little understood. We explore the social impacts arising from the establishment of an MPA using Lyme Bay (south west England) as a case study. Through a series of small group semi-structured interviews the social impacts experienced by fishermen (mobile and static gear), recreational users (divers and sea anglers) and recreation service providers (charter boat and dive businesses) were explored. The social impacts expressed varied according to activity in which the stakeholder group engaged. Negative themes included lengthening fishing trips, tension and conflict, fishermen identity, equity and uncertainty in the long-term. Positive themes included improved experiences for both commercial fishermen and recreational users, and expectations for long-term benefits. These impacts need to be understood because they influence stakeholder behaviour. Failure to interpret stakeholder responses may lead to poor decision-making and worsening stakeholder relations. These findings have implications for the success of the MPA in Lyme Bay, but also for the future network of marine conservation zones around the UK. Any assessment of MPA impacts must therefore identify social as well as economic and environmental change.