Carbon-13 magnetic resonance spectroscopy

High-resolution, natural-abundance ¹³C spectra have been obtained from a wide variety of organic compounds; ¹³C chemical shifts and coupling constants have been correlated with other molecular properties.

Geminal and vicinal, carbon-proton couplings in benzene and the five- and six-membered aromatic heterocycles have been related to the corresponding proton-proton couplings in substituted ethylenes. The carbon-proton coupling constants in benzene are J_CCH = + 1.0, J_CCCH = +7.4 and J_CCCH = -1.1 Hz. Extended Hückel wavefunctions are uniformly poor in explaining the long-range, carbon-proton couplings in aromatic systems.

Couplings between carbon and elements other than hydrogen have been observed in proton decoupled ¹³C spectra. All of the carbons in fluorobenzene and 1-fluoronaphthalene, but only six of the carbons in 2-fluoronaphthalene are coupled to the fluorine. One-bond, carbon-phosphorus coupling in trialkylphosphines is negative, while one-bond, carbon-phosphorus coupling in tetra-alkylphosphonium ions is positive. Atoms which do not use hybrid orbitals to form bonds to carbon (F, P(III), Se, Te) may have negative, one-bond coupling constants because of the failure of the average energy approximation. One-bond couplings between carbon and carbon, silicon, tin, lead and mercury appear to be explainable in terms of an effective nuclear charge and the s-bond order of the metal. Couplings between carbon and nitrogen and phosphorus (IV) have significant negative contributions to the Fermi contact coupling expression, though, within one series, correlations with s-bond order may be valid. Carbon-carbon coupling in cyclopropane derivatives (10-15 Hz) is consistent with a high degree of p character in the interior orbitals. Some two- and three-bond carbon-carbon coupling constants have also been observed.

Substituent effects of hydroxyl groups on the ¹³C chemical shifts of continuous-chain alkanes depend both on steric and electronic factors. The hydroxyl substituent effects in the long-chain, primary alcohols are α = -48.3, β = -10.2, and γ = +6.0 ppm. The upfield γ effect is attributed to steric crowding in the gauche conformations. Additivity of the hydroxyl and carbonyl and alkyl substituent effects in alkyl-substituted cyclohexanols and cyclohexanones has been demonstrated.

San Pedro berraktibatzen

Pasai San Pedroko Herrikoplaza-ko inguruaren birplanteaketa erabilera berrien integrazioaren eta irisgarritasunaren hobekuntzaren bidez.

Futboleko oinarrizko talde batean, periodizazio proposamen berri bat

Periodizazio taktikoa, futbol alorrean Victor Frade irakasle portugaldarraren eskutik orain dela 30 urte sortu zen entrenamendu metodologia bat da, gaur egun, gehien bat Jose Mourinhok, honen bidez lortu dituen garaipen eta lorpenak direla eta, mundu mailako futbolean, hedapen eta gorentasun bat izatera lortu duelarik. Jokatzeko erara bideratua dagoen entrenamendua honen oinarria izanik, jadanik zeuden beste metodologia entrenamenduak kolokan jartzera iristen da, besteak beste, jokoaren elementu ezberdinen banantze eta indibidualizazioan oinarritzen ziren metodologiak. Lan honen helburua, entrenatzeko eta futbola ikusteko ikuspegia aldatzen duen entrenamendu metodologia moderno honek, aspektu fisiko-taktikoan, beste metodologia baten aurrean, eredu integratuarekiko dituen ezberdintasunak, saioetan nahiz partiduetan duten emaitza alderatzea da. Horretarako, Espainiako Futbol Hirugarren Mailako, talde batekin eraman da ikerketa aurrera, jokalariek Pse-saio metodoaren bitartez emandako kargaren datuak erabiliz.

Judoaren barneratze prozesurako ebaluazio tresna berri bat

Judoaren ezaguera teknikoa aldera batera utzita ikuspegi orokorrago bat garatzean oinarritzen da.

Pilotariaren profil teknikoa hobetzeko proposamena

Lan honen bitartez, pilotarien profil teknikoa hobetzeko proposamena egin dut, non denboraldia fase ezberdinetan banandurik, bakoitzean landu beharreko edukiak eta lortu beharreko helburuak ageri diren.

Incidencia de las Revoluciones en los Movimientos Sociales Transnacionales. El Caso de la Revolución Cubana y su Influencia en el Movimiento Antiglobalización

328 p.

Patterns of growth, mortality, and size of the tropical damselfish Acanthochromis polyacanthus across the continental shelf of the Great Barrier Reef

Age-based analyses were used to demonstrate consistent differences in growth between populations of Acanthochromis polyacanthus (Pomacentridae) collected at three distance strata across the continental shelf (inner, mid-, and outer shelf) of the central Great Barrier Reef (three reefs per distance stratum). Fish had significantly greater maximum lengths with increasing distance from shore, but fish from all distances reached approximately the same maximum age, indicating that growth is more rapid for fish found on outer-shelf reefs. Only one fish collected from inner-shelf reefs reached >100 mm SL, whereas 38−67% of fish collected from the outer shelf were >100 mm SL. The largest age class of adult-size fish collected from inner and mid-shelf locations comprised 3−4 year-olds, but shifted to 2-year-olds on outer-shelf reefs. Mortality schedules (Z and S) were similar irrespective of shelf position (inner shelf: 0.51 and 60.0%; mid-shelf: 0.48 and 61.8%; outer shelf: 0.43 and 65.1%, respectively). Age validation of captive fish indicated that growth increments are deposited annually, between the end of winter and early spring. The observed cross-shelf patterns in adult sizes and growth were unlikely to be a result of genetic differences between sample populations because all fish collected showed the same color pattern. It is likely that cross-shelf variation in quality and quantity of food, as well as in turbidity, are factors that contribute to the observed patterns of growth. Similar patterns of cross-shelf mortality indicate that predation rates varied little across the shelf. Our study cautions against pooling demographic parameters on broad spatial scales without consideration of the potential for cross-shelf variabil

Response of the topological surface state to surface disorder in TlBiSe2

Through a combination of experimental techniques we show that the topmost layer of the topological insulator TlBiSe2 as prepared by cleavage is formed by irregularly shaped Tl islands at cryogenic temperatures and by mobile Tl atoms at room temperature. No trivial surface states are observed in photoemission at low temperatures, which suggests that these islands cannot be regarded as a clear surface termination. The topological surface state is, however, clearly resolved in photoemission experiments. This is interpreted as direct evidence of its topological self-protection and shows the robust nature of the Dirac cone-like surface state. Our results can also help explain the apparent mass acquisition in S-doped TlBiSe2.

Cuba em transformação: socialismo e as reformas econômicas do 6 Congresso do Partido Comunista

Esta dissertação reflete sobre os dilemas do socialismo contemporâneo a partir da experiência revolucionária cubana, focalizando especialmente a etapa conhecida como "atualização do socialismo". Em 2011 o VI Congresso do Partido Comunista de Cuba aprovou um conjunto de reformas econômicas cuja meta proclamada é a "atualização do modelo econômico e social" do país. Nestes termos, a proposta central do governo aponta para a diversificação dos atores econômicos e maiores níveis de descentralização, entretanto, sem abrir mão do predomínio da propriedade estatal sobre os meios de produção e da planificação sobre o mercado. Por outro lado, inegavelmente, essas medidas trazem mudanças significativas em relação ao modelo socialista historicamente construído em Cuba. Visando entender esse processo de transformações, o presente trabalho abordará os aspectos políticos e teóricos destas reformas.

Evaluation of the economic costs and benefits of methods for reducing nutrient loads to the Gulf of Mexico: Topic 6 Report for the Integrated Assessment on Hypoxia in the Gulf of Mexico.

In this report we analyze the Topic 5 report’s recommendations for reducing nitrogen losses to the Gulf of Mexico (Mitsch et al. 1999). We indicate the relative costs and cost-effectiveness of different control measures, and potential benefits within the Mississippi River Basin. For major nonpoint sources, such as agriculture, we examine both national and basin costs and benefits. Based on the Topic 2 economic analysis (Diaz and Solow 1999), the direct measurable dollar benefits to Gulf fisheries of reducing nitrogen loads from the Mississippi River Basin are very limited at best. Although restoring the ecological communities in the Gulf may be significant over the long term, we do not currently have information available to estimate the benefits of such measures to restore the Gulf’s long-term health. For these reasons, we assume that measures to reduce nitrogen losses to the Gulf will ultimately prove beneficial, and we concentrate on analyzing the cost-effectiveness of alternative reduction strategies. We recognize that important public decisions are seldom made on the basis of strict benefit–cost analysis, especially when complete benefits cannot be estimated. We look at different approaches and different levels of these approaches to identify those that are cost-effective and those that have limited undesirable secondary effects, such as reduced exports, which may result in lost market share. We concentrate on the measures highlighted in the Topic 5 report, and also are guided by the source identification information in the Topic 3 report (Goolsby et al. 1999). Nonpoint sources that are responsible for the bulk of the nitrogen receive most of our attention. We consider restrictions on nitrogen fertilizer levels, and restoration of wetlands and riparian buffers for denitrification. We also examine giving more emphasis to nitrogen control in regions contributing a greater share of the nitrogen load.

Reproduction and recruitment of white mullet (Mugil curema) to a tropical lagoon (Margarita Island, Venezuela) as revealed by otolith microstructure

The reproductive activity and recruitment of white mullet (Mugil curema) was determined by observations of gonad development and coastal juvenile abundance from March 1992 to July 1993. Adults were collected from commercial catches at three sites in northeastern Venezuelan waters. Spawning time was determined from the observation of macroscopic gonadal stages. Coastal recruitment was determined from fish samples collected biweekly by seining in La Restinga Lagoon, Margarita Island, Venezuela. The examination of daily growth rings on the otoliths of coastal recruits was used to determine their birth date and estimate the period of successful spawning. Fish with mature gonads were present throughout the year but were less frequent between September and January when spawning individuals migrated offshore. In both years, juvenile recruitment to the lagoon was highest between March and June when high densities of 25–35 mm juveniles were observed. Back-calculated hatching-date frequency distributions revealed maximum levels of successful spawning in December–January that were significantly correlated with periods of enhanced upwelling. The relation between the timing of successful spawning and the intensity of coastal recruitment in white mullet was likely due to variations in food availability for first-feeding larvae as well as to variations in the duration of the transport of larvae shoreward as a result of varying current conditions associated with upwelling.

Effect of some physico-chemical factors on the survival and growth of Penaeus monodon postlarvae

Growth and survival rates of P. monodon postlarvae were examined at different temperatures, salinities, and nitrite and ammonia concentrations, using one feed level. Condition of postlarvae greatly affected the experimental results shown in some instances where very low survival rates were obtained, even for the controls. Results indicated that postlarvae from PSUB-10 and up can tolerate salinity changes of 10 to 20 ppt without prior acclimation. Survival generally appears the same for temperatures between 24 and 36 C. It appears that P. monodon postlarvae have higher temperature tolerance. Tolerance of postlarvae at the early postlarval stage is between 30 and 50 ppm of nitrate. They were more tolerant from PSUB-10 upwards. Although survival was high in runs containing nitrite, growing appears to have been affected. Postlarvae could tolerate ammonia concentrations up to about 50 ppm. At 100 ppm higher mortality rates were observed. Whether or not there was any permanent effect by nitrate and ammonia at high but apparently tolerable levels is not known.

Effect of nitrite, ammonia, and temperature on P. monodon larvae

P. monodon larvae were studied for the effects of temperature, ammonia, and nitrite on survival. Toxicity levels of nitrite were found to vary with larval stage. Larvae could tolerate ammonia up to about 10 ppm, with the effect more clearly shown by the zoea stage. Survival and growth were not significantly affected by temperature, although moulting was enhanced at temperatures higher than 29 C. Larvae of P. monodon have lower tolerance toward nitrite and ammonia compared to postlarvae. Although high survival was obtained at low levels of nitrite and ammonia, it is still necessary to know their effects on metabolism, in order to examine possible biochemical parameters for diagnosing sublethal toxicity or stress.