Apparent shortening of the Csp(3)-Csp(3) bond analysed via a variable-temperature X-ray diffraction study in racemic 1,1 '-binaphthalene-2,2 '-diyl diethyl bis(carbonate)

Crystal structure determination at room temperature [292 (2) K] of racemic 1,1'-binaphthalene-2,2'-diyl diethyl bis(carbonate), C26H22O6, showed that one of the terminal carbon-carbon bond lengths is very short [Csp(3)-Csp(3) = 1.327 (6) angstrom]. The reason for such a short bond length has been analysed by collecting data sets on the same crystal at 393, 150 and 90 K. The values of the corrected bond lengths clearly suggest that the shortening is mainly due to positional disorder at two sites, with minor perturbations arising as a result of thermal vibrations. The positional disorder has been resolved in the analysis of the 90 K data following the changes in the unit-cell parameters for the data sets at 150 and 90 K, which appear to be an artifact of a near centre of symmetry relationship between the two independent molecules in the space group P (1) over bar at these temperatures. Indeed, the unit cell at low temperature (150 and 90 K) is a supercell of the room-temperature unit cell.

Overwintering ecology of northern field layer plants : snow and photosynthesis in Vaccinium vitis-idaea L.

Winter is a significant period for the seasonality of northern plants, but is often overlooked when studying the interactions of plants and their environment. This study focuses on the effects of overwintering conditions, including warm winter periods, snow, and snowmelt on boreal and sub-Arctic field layer plants. Wintertime photosynthesis and related physiological factors of evergreen dwarf shrubs, particularly of Vaccinium vitis-idaea, are emphasised. The work combines experiments both in the field and in growth chambers with measurements in natural field conditions. Evergreen dwarf shrubs are predominantly covered by snow in the winter. The protective snow cover provides favourable conditions for photosynthesis, especially during the spring before snowmelt. The results of this study indicate that photosynthesis occurs under the snow in V. vitis-idaea. The light response of photosynthesis determined in field conditions during the period of snow cover shows that positive net CO2 exchange is possible under the snow in the prevailing light and temperature. Photosynthetic capacity increases readily during warm periods in winter and the plants are thus able to replenish carbohydrate reserves lost through respiration. Exposure to low temperatures in combination with high light following early snowmelt can set back photosynthesis as sustained photoprotective measures are activated and photodamage begins to build up. Freezing may further decrease the photosynthetic capacity. The small-scale distribution of many field layer plants, including V. vitis-idaea and other dwarf shrubs, correlates with the snow distribution in a forest. The results of this study indicate that there are species-specific differences in the snow depth affinity of the field and ground layer species. Events and processes taking place in winter can have a profound effect on the overall performance of plants and on the interactions between plants and their environment. Understanding the processes involved in the overwintering of plants is increasingly important as the wintertime climate in the north is predicted to change in the future.

Photosynthesis of ground vegetation in boreal Scots pine forests

Research on carbon uptake in boreal forests has mainly focused on mature trees, even though ground vegetation species are effective assimilators and can substantially contribute to the CO2 uptake of forests. Here, I examine the photosynthesis of the most common species of ground vegetation in a series of differently aged Scots pine stands, and at two clear-cut sites with substantial differences in fertility. In general, the biomass of evergreen species was highest at poor sites and below canopies, whereas grasses and herbs predominated at fertile sites and open areas. Unlike mosses, the measured vascular species showed clear annual cycles in their photosynthetic activity, which increased earlier and decreased later in evergreen vascular species than in deciduous species. However, intraspecific variation and self-shading create differences in the overall level of photosynthesis. Light, temperature history, soil moisture and recent possible frosts could explain the changes in photosynthesis of low shrubs and partially also some changes in deciduous species. Light and the occurrence of rain events explained most of the variation in the photosynthesis of mosses. The photosynthetic production of ground vegetation was first upscaled, using species-specific and mass-based photosynthetic activities and average biomass of the site, and then integrated over the growing season, using changes in environmental factors. Leaf mass-based photosynthesis was highest in deciduous species, resulting in notably higher photosynthetic production at fertile sites than at poor clear-cut sites. The photosynthetic production decreased with stand age, because flora changed towards evergreen species, and light levels diminished below the canopy. In addition, the leaf mass-based photosynthetic activity of some low shrubs declined with the age of the surrounding trees. Different measuring methods led to different momentary rate of photosynthesis. Therefore, the choice of measuring method needs special attention.

Efficient energy transport in photosynthesis: roles of coherence and entanglement

Recently it has been discovered---contrary to expectations of physicists as well as biologists---that the energy transport during photosynthesis, from the chlorophyll pigment that captures the photon to the reaction centre where glucose is synthesised from carbon dioxide and water, is highly coherent even at ambient temperature and in the cellular environment. This process and the key molecular ingredients that it depends on are described. By looking at the process from the computer science view-point, we can study what has been optimised and how. A spatial search algorithmic model based on robust features of wave dynamics is presented.

Sustainability of apparent slip in micro-channel flows

In the present work, we experimentally study the flow of water over textured hydrophobic surfaces in a micro-channel. Shear stress measurements are done along with direct visualization of trapped air pockets on the hydrophobic surface. The trapped air pockets on such surfaces are known to be responsible for apparent slip at these surfaces and hence in significant drag reduction. In typical circumstances, the apparent slip reduces over time as seen, for example, from our shear stress measurements. This implies that the drag reduction will not be sustained. We have performed extensive visualizations of the trapped air pockets while varying flow parameters like the flow rate and the pressure. We present here direct visualizations that show that under some conditions, the air pockets can grow with time. The variation of the air pocket size with time is found to change qualitatively and quantitatively as the flow rate is varied. These measured changes in the air pocket size with time have a direct bearing on the sustainability of apparent slip in micro-channel flows.

Between photocatalysis and photosynthesis: Synchrotron spectroscopy methods on molecules and materials for solar hydrogen generation

Energy research is to a large extent materials research, encompassing the physics and chemistry of materials, including their synthesis, processing toward components and design toward architectures, allowing for their functionality as energy devices, extending toward their operation parameters and environment, including also their degradation, limited life, ultimate failure and potential recycling. In all these stages, X-ray and electron spectroscopy are helpful methods for analysis, characterization and diagnostics for the engineer and for the researcher working in basic science.This paper gives a short overview of experiments with X-ray and electron spectroscopy for solar energy and water splitting materials and addresses also the issue of solar fuel, a relatively new topic in energy research. The featured systems are iron oxide and tungsten oxide as photoanodes, and hydrogenases as molecular systems. We present surface and subsurface studies with ambient pressure XPS and hard X-ray XPS, resonant photoemission, light induced effects in resonant photoemission experiments and a photo-electrochemical in situ/operando NEXAFS experiment in a liquid cell, and nuclear resonant vibrational spectroscopy (NRVS). (C) 2012 Elsevier B.V. All rights reserved.

Artificial photosynthesis and the splitting of water to generate hydrogen

It is no exaggeration to state that the energy crisis is the most serious challenge that we face today. Among the strategies to gain access to reliable, renewable energy, the use of solar energy has clearly emerged as the most viable option. A promising direction in this context is artificial photosynthesis. In this article, we briefly describe the essential features of artificial photosynthesis in comparison with natural photosynthesis and point out the modest success that we have had in splitting water to produce oxygen and hydrogen, specially the latter.

Some factors affecting the distribution and apparent abundance of yellowfin and skipjack tuna in the Eastern Pacific Ocean

ENGLISH: Since 1951, the Inter-American Tropical Tuna Commission has been investigating the biology, ecology and population dynamics of the yellowfin tuna, Thunnus albacares, and the skipjack tuna, Katsuwonus pelamis, in the Eastern Pacific Ocean. Of particular importance has been the study of the effects of fishing and of fishery-independent factors on the abundance and distribution of these tunas. For yellowfin tuna there is, on the average, an inverse relationship between total fishing effort and apparent abundance (Schaefer, 1957a). For skipjack there is no evidence to suggest that fishing effort has ever been sufficiently intense to affect measurably the abundance (Schaefer, 1961). Rather, it appears that the year-to-year fluctuations in apparent abundance are independent of the activities of the fishing fleets. SPANISH: Desde 1951 la Comisión Interamericana del Atún Tropical se ha dedicado a la investigación de la biología, ecología y la dinámica de las poblaciones del atún aleta amarilla, Thunnus albacares, y del barrilete, Katsuwonus pelamis, en el Océano Pacífico del Este. De importancia especial ha sido el estudio de los efectos de la pesca y de los factores independientes de las pesquerías sobre la abundancia y la distribución de esos atunes. En cuanto al atún aleta amarilla, existe, en promedio, una relación inversa entre el esfuerzo total de pesca y la abundancia aparente (Schaefer, 1957a) . Con respecto al barrilete, no hay evidencia que haga pensar que el esfuerzo de pesca haya sido nunca lo suficientemente intenso como para afectar sensiblemente la abundancia (Schaefer, 1961). Más bien parece que las fluctuaciones de un año a otro en su abundancia aparente, son independientes de las actividades de las flotas pesqueras.

Sea surface temperature and the distribution and apparent abundance of skipjack (Katsuwonus pelamis) in the Eastern Pacific Ocean, 1951-1968

ENGLISH: Isograms of sea surface temperature (OC) have been produced for 1949-1968 for the areas of the eastern Pacific Ocean in which the majority of the skipjack catch is taken. These are in the immediate coastal zone, California (35° N) to Chile (20 0 S), and the Revillagigedo and Galapagos Islands groups. Skipjack occurrence and apparent abundance (as CSDF, i.e., catch per standard days fishing, standardized in purse-seiner units) for 1951-1968 were then superimposed on the surface temperature isograms. Results show that skipjack occur at surface temperatures> 17° C but with the majority between 20°-30° C. Apparent abundance at CSDF > 1 ton/day is normally Iimited to 20°29° C water, except in two areas in certain years; from the Gulf of Tehuantepec to Cape Mala rates of 1-9 tons/day are relatively common at 29°-30° C, and off Chimbote (Peru) occasionally >9 tons/day are recorded down to 18° C. As expected there were no apparent relationships between annual thermal conditions in the coastal zone and skipjack abundance (total catch or indices of abundance) in the same or 2 subsequent years. An Appendix to the report determines the quantitative relationships between surface temperature and skipjack abundance in relatively small areal strata in Baja California waters in 1955 and 1958. Relationships generally appeared significant and opposite in these years when temperatures were respectively anomalously cold and warm. SPANISH: Se han producido isogramas de la temperatura de la superficie del mar (OC) para 1949-1968 correspondientes a las áreas del Océano Pacífico oriental en donde se obtiene la mayor parte de la captura de barrilete. Estas se encuentran ubicadas en la zona costanera inmediata, desde California (35°N) hasta Chile (200S) y en las Islas Revillagigedo y Galápagos. La ocurrencia de barrilete y su abundancia aparente (expresada como CDSP standardizada en unidades de cerqueros) para 1951-1968 fueron luego superpuestas en los isogramas de la temperatura superficial. Los resultados demuestran que el barrilete aparece en temperaturas superficiales de > 17°C pero la mayoría entre los 20°C-30°C. La abundancia aparente de la CDSP > 1 tonelada/día se limita normalmente a aguas de 20°-29°C, excepto en dos áreas en ciertos años; desde el Golfo de Tehuantepec a Cabo Mala las tasas de 1-9 toneladas/día son relativamente comunes en los 29°-30°C, y frente a Chimbote (Perú) se registran ocasionalmente> 9 toneladas/día a una temperatura tan fría como de 18°C. Como era de esperarse no existió una relación aparente entre las condiciones térmicas anuales de la zona costanera y la abundancia del barrilete (captura total o índices de abundancia) en el mismo año o en los 2 años siguientes. Un Apéndice del informe determina la relación cuantitativa entre la temperatura superficial y la abundancia del barrilete en un estrato de áreas relativamente pequeño en las aguas de Baja California en 1955 y 1968. Las relaciones generalmente aparecieron significativas y opuestas en esos años cuando las temperaturas fueron respectivamente anómalamente frías y calientes. (PDF contains 53 pages.)

The influence of some environmental variables on the apparent abundance of skipjack tuna, Katsuwonus pelamis, in the Eastern Pacific Ocean

ENGLISH: The abundance of skipjack larvae in the central and western Pacific approximately doubled for every 1°C increase in sea-surface temperature (SST) from 23°C to a maximum of about 29°C, and then usually decreased with further increases in SST. Skipjack larvae are scarce in the eastern Pacific Ocean (EPO), so most skipjack recruits and adults in this area are believed to have originated in the central and, possibly, the western Pacific. The catch per unit of effort (CPUE), in short tons per day's fishing, and the catch rate, in number of fish per day's fishing, are estimates of apparent abundance in a fishery. The logarithm of the annual CPUE for skipjack for international baitboats in the EPO for the 1934-1960 period was positively correlated with SST in the spawning area in the central Pacific 18 months earlier (r2 0.31), during the July-June period when most of the recruits in each cohort were presumed to have been spawned. Adequate data for other environmental variables were not available for testing with the baitboat data. The other environmental variables available and selected for testing for correlation with estimates of skipjack abundance for purse seiners for the 1961-1984 period and the reasons for their selection are as follows. 1)Wind-mixing index (WMI). The degree of mixing in the upper layers of the ocean is proportional to the cube of the wind speed, called WMI. The degree of mixing in the spawning areas of the central and the western Pacific may affect the concentration of organisms that skipjack larvae feed upon, thereby influencing their survival, and ultimately determining cohort strength and the number of recruits to the eastern Pacific fishery. 2) SST in the fishing areas at the time of fishing (SST). The CPUE for yellowfin tuna has been shown to be inversely related to SST in the fishing areas, and there are indications that skipjack CPUE is lower during EI Nino events when SST is higher than normal. 3) North-south SST gradient across the thermal front off the Gulf of Guayaquil. This is a measure of the degree of upwelling and nutrient enrichment of the upper waters south of the front and ultimately of the production of food for tunas. 4) Speed of the North Equatorial Countercurrent (NECC). Young skipjack may migrate from the central Pacific to the EPO in the eastward flowing NECC; if so, the number of recruits might be affected by variations in the speed of the current. The logarithm of the annual catch rate of skipjack recruits by international purse seiners in the EPO for the 1961-1984 period was positively correlated with SST in the spawning area of the central Pacific 18 months earlier (r2 = 0.21),and inversely correlated with WMI in the spawning area 18 months earlier (r2 0.46). The logarithm of CPUE for purse seiners in the area off the Gulf of Guayaquil was not correlated with SST in the spawning area 18 months earlier, but was inversely correlated with WMI in the spawning area 18 months earlier (r2 = 0.19), and inversely correlated with the north-south SST gradient in the fishing area at the time of fishing (r2 0.32). Neither of these estimates of apparent abundance from purse seiners were correlated with SST in the fishing areas, or with the speed of the NECC at earlier times. SPANISH: La abundancia de larvas de barrilete en el Pacífico central y occidental se multiplicó por dos, aproximadamente, por cada aumento de 1°Cen la temperatura de la superficie del mar (TSM) entre 23°C y un máximo de unos 29°C, y luego generalmente disminuyó con más aumentos en la TSM. Las larvas de barrilete son escasas en el Océano Pacífico oriental (OPO), y por lo tanto se cree que la mayoría de los reclutas y adultos en esta zona surgieron del Pacífico central, y posiblemente también del Pacífico occidental. La captura por unidad de esfuerzo (CPUE), en toneladas cortas por día de pesca, y la tasa de captura, en número de peces por día de pesca, son estimaciones de la abundancia aparente en una pesquería. El logaritmo de la CPUE anual de barrilete lograda por barcos de carnada en el OPO en el período 1934-1960 se correlacionó positivamente con la TSM en la zona de desove en el Pacífico central de 18 meses antes (r2 = 0.31), durante el período de junio-julio en el cual se cree que nació la mayoría de los reclutas en cada cohorte. No se dispuso de datos suficientes sobre otras variables ambientales para comprobarlos con los datos de los barcos de carnada. Las demás variables ambientales disponibles y seleccionadas para someterlas a pruebas de correlación con las estimaciones de la abundancia del barrilete de barcos cerqueros en el período 1961-1984, y las razones por su selección, son las siguientes: 1) Indice de mezcla por el viento (IMV). El grado de mezcla en las capas superiores del océano es proporcional al cubo de la velocidad del viento, llamado IMV. Es posible que el grado de mezcla en las zonas de desove del Pacífico central y occidental afecte la concentración de los organismos que alimentan a las larvas del barrilete, afectando así la supervivencia de éstas, y finalmente determinando el tamaño de las cohortes y el número de reclutas a la pesquería del OPO. 2) TSM en la zona de pesca al realizarse la pesca (TSM). Se ha mostrado que la relación de la CPUE del atún aleta amarilla a la TSM en la zona de pesca es inversa, y existen indicaciones que la CPUE de barrilete es inferior durante eventos del Niño, cuando las TSM son superiores a lo normal. 3) Gradiente norte-sur de las TSM a través del frente térmico frente al Golfo de Guayaquil. Esto es una medida del grado de afloramiento y enriquecimiento nutritivo del nivel superior de las aguas al sur de dicho frente, y finalmente de la producción de alimento para los atunes. 4) La velocidad de la Contracorriente Ecuatorial del Norte (CCEN). Es posible que los bariletes juveniles migren del Pacífico central al Pacífico oriental en la CCEN, que fluye hacia el este; de ser así, es posible que la cantidad de reclutas se vea afectada por variaciones en la velocidad de la corriente. El logaritmo de la tasa anual de captura de reclutas de barrilete por cerqueros de varias banderas en el OPO en el período 1961-1964 estuvo correlacionado de forma positiva con las TSM en la zona de desove del Pacífico central de 18meses antes (r2 0.21),y de forma inversa con el IMV de la zona de desove de 18 meses antes (r2 0.46). El logaritmo de la CPUE de los cerqueros en la zona frente al Golfo de Guayaquil no estuvo correlacionado con las TSM en la zona de desove de 18 meses antes, pero sí estuvo correlacionado de forma inversa con el IMV en la zona de desove de 18 meses antes (r2 0.19),y con el gradiente norte-sur de las TSM en la zona de pesca al realizarse la pesca (r2 0.32). Ninguna de estas estimaciones de abundancia aparente provenientes de barcos cerqueros estuvo correlacionada con las TSM en las zonas de pesca o con la velocidad de la CCEN en épocas anteriores. (PDF contains 140 pages.)