Rates of electronic energy transfer in conformationally flexible bichromophoric macrocyclic complexes: a combined experimental and molecular modeling study

Electronic energy transfer (EET) rate constants between a naphthalene donor and anthracene acceptor in [ZnL4a](ClO4)(2) and [ZnL4b](ClO4)(2) were determined by time-resolved fluorescence where L-4a and L-4b are the trans and cis isomers of 6-((anthracen-9-yl-methyl)amino)-6,13-dimethyl-13-((naphthalen-1-yl-methyl)amino)-1,4,8,11-tetraazacyclotetradecane, respectively. These isomers differ in the relative disposition of the appended chromophores with respect to the macrocyclic plane. The trans isomer has an energy transfer rate constant (k(EET)) of 8.7 x 10(8) s(-1), whereas that of the cis isomer is significantly faster (2.3 x 10(9) s(-1)). Molecular modeling was used to determine the likely distribution of conformations in CH3CN solution for these complexes in an attempt to identify any distance or orientation dependency that may account for the differing rate constants observed. The calculated conformational distributions together with analysis by H-1 NMR for the [ZnL4a](2+) trans complex in the common trans-III N-based isomer gave a calculated Forster rate constant close to that observed experimentally. For the [ZnL4b](2+) cis complex, the experimentally determined rate constant may be attributed to a combination of trans-Ill and trans-I N-based isomeric forms of the complex in solution.

Surface diffusion of strongly adsorbing vapors in activated carbon by a differential permeation method

Conventional methods to determine surface diffusion of adsorbed molecules are proven to be inadequate for strongly adsorbing vapors on activated carbon. Knudsen diffusion permeability (B-k) for strongly adsorbing vapors cannot be directly estimated from that of inert gases such as helium. In this paper three models are considered to elucidate the mechanism of surface diffusion in activated carbon. The transport mechanism in all three models is a combination of Knudsen diffusion, viscous flow and surface diffusion. The collision reflection factor f (which is the fraction of molecules undergoing collision to the solid surface over reflection from the surface) of the Knudsen diffusivity is assumed to be a function of loading. It was found to be 1.79 in the limit of zero loading, and decreases as loading increases. The surface diffusion permeability increases sharply at very low pressures and then starts to decrease after it has reached a maximum (B(mum)s) at a threshold pressure. The initial rapid increase in the total permeability is mainly attributed to surface diffusion. Interestingly the B(mum)s for all adsorbates appear at the same volumetric adsorbed phase concentration, suggesting that the volume of adsorbed molecules may play an important role in the surface diffusion mechanism in activated carbon. (C) 2003 Elsevier Ltd. All rights reserved.

Field hydraulic properties of an Alfisol under various fallow systems in southwestern Nigeria

The effects of various fallow management systems and cropping intensities on water infiltration were measured on an Alfisol at Ibadan in southwestern Nigeria. The objective was to determine the influence of the land use systems (a combination of crop-fallow sequences and intercropping types) on soil hydraulic properties obtained by disc permeameter and double-ring infiltration measurements. The experiment was established in 1989 as a split-plot design with four replications. The main plots were natural fallow, planted Pueraria phaseoloides and planted Leucaena leucocephala. The subplots were 1 year of maize/cassava intercrop followed by 3-year fallow (25% cropping intensity), or 2-year fallow (33% cropping intensity), or 1-year fallow (50% cropping intensity), or no fallow period (100% cropping intensity). Water infiltration rates and sorptivities were measured under saturated and unsaturated flow. Irrespective of land use, infiltration rates at the soil surface (121-324 cm h(-1)) were greater than those measured at 30 cm depth (55-144 cm h(-1)). This indicated that fewer large pores were present below 30 cm depth compared with 0-30 cm, depth. Despite some temporal variation, sorptivities with the highest mean value of 93.5 cm h(-1/2) increased as the cropping intensity decreased, suggesting a more continuous macropore system under less intensive land use systems. This was most likely due to continuous biopores created by perennial vegetation under long fallow systems. Intercropped maize and cassava yields also increased as cropping intensity decreased. The weak relationship between crop yields and hydraulic conductivity/infiltration rates suggests that the rates were not limiting.

A technique to assess small-scale heterogeneity of chemical properties in soil aggregates

A new method is presented which allows the separation of the soil aggregate exterior from the aggregate core. The method employs a combination of aggregate freezing with rapid separation of aggregate exteriors using ultrasonic energy. The factors influencing the thickness of the removed aggregate surface layer include water content of the aggregate prior to freezing, temperature difference between that of the frozen aggregate and that of the liquid it is submerged in during sonification, sonification time and energy, and the type of the immersion liquid. The success of the method and the thickness of the removed aggregate surface were examined using barium ( Ba2+) as a tracer. Barium ( as BaCl2) is rapidly absorbed by soil and is present at only very low levels in natural soils. Surface layers of 0.2 - 0.4 cm thickness were successfully removed from aggregates of 1 - 4 cm diameter. Two examples are given from soils in northern NSW to demonstrate the occurrence of small- scale heterogeneity in soil chemical properties. Compared with the surface fraction, a 4 - 7% higher calcium concentration was found in the core fraction of a clay loam soil ( Dermosol). Conversely, on a cracking clay soil ( Vertosol), atrazine concentration was around 15 times greater in the aggregate surface fractions compared with core fractions. Compared with the traditional estimation of soil chemical properties on homogenised bulk soil samples, it is suggested that separate analysis of aggregate surface and core fractions could provide useful additional information on the relationships between soil properties and environmental responses.

Variation of the crystalline structure of coal char during gasification

The variation of the crystallite structure of several coal chars during gasification in air and carbon dioxide was studied by high-resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD) techniques. The XRD analysis of the partially gasified coal chars, based on two approaches, Scherrer's equation and Alexander and Sommer's method, shows a contradictory trend of the variation of the crystallite height with carbon conversion, despite giving a similar trend for the crystallite width change. The HRTEM fringe images of the partially gasified coal chars indicate that large and highly ordered crystallites exist at conversion levels as high as 86%. It is also demonstrated that the crystalline structure of chars can be very different although their pore structures are similar, suggesting a combination of crystalline structure analysis with pore structure analysis in studies of carbon gasification.

Hydrodynamic origin of diffusion in nanopores

We study the transport of a subcritical Lennard-Jones fluid in a cylindrical nanopore, using a combination of equilibrium and nonequilibrium as well as dual control volume grand canonical molecular dynamics methods. We show that all three techniques yield the same value of the transport coefficient for diffusely reflecting pore walls, even in the presence of viscous transport. We also demonstrate that the classical Knudsen mechanism is not manifested, and that a combination of viscous flow and momentum exchange at the pore wall governs the transport over a wide range of densities.

Identity and the concept of the West: the case of Brazil and India

This study aims to provide insights about how Brazil and India view and relate to the concept of the West, and how this affects their identity and foreign policy. Both countries' notions about the West are the subject of lively domestic discussion both in academia and the media, reflecting the struggle these countries find themselves in to define their identity as they rise. I argue that the concept of the West serves, in both Brazil and India, as a crucial concept to articulate their own identity-by a complex combination of criticizing, distancing itself from, or attempting to emulate the West.

Initial growth of maize in response to application of rock phosphate, vermicompost and endophytic bacteria

Due to the high energy requirement and demand for non-renewable resources for the production of chemical fertilizers, added also to the environmental impact caused by the use of such products, it is important to intensify research on bio-based agricultural inputs. The use of nitrogen-fixing endophytic and phosphate solubilizing bacteria can provide these nutrients to the plants from the air and poorly soluble phosphorus sources, such as phosphate rock. The objective of this study was to evaluate the nutrition and initial growth of maize (Zea mays L.) in response to the inoculation of nitrogen-fixing and rock phosphate solubilizing endophytic bacteria, in single or mixed formulation, applied with vermicompost. The treatments containing bacteria, both diazotrophic and phosphate solubilizing, when compared to controls, showed higher levels of leaf nitrogen and phosphorus in maize, as well as higher growth characteristics. The application of vermicompost showed synergistic effect when combined with endophytic bacteria. Thus, the innovation of the combination of the studied factors may contribute to the early development of maize.

Use of biofilm in the postharvest conservation of 'Pedro Sato' guava

This present work aimed to assess the effect of different concentrations of cassava starch, associated or not with prochloraz fungicide, on the postharvest conservation of 'Pedro Sato' guavas. Physiologically mature fruits were immersed in a solution of prochloraz (49.5 g/100 liters of water) for 5 min. Fruit treated with distilled water and air dried were used as control. They were immersed in cassava starch suspension at concentrations of 0, 20, 30 and 40 g/L, plus 0.5 mL/L of mineral oil. The fruits were stored at 21.0 ± 1.0 ºC and relative humidity of 85 ± 5%, for 12 days, and were examined at every three days. The combination of prochloraz and cassava starch resulted in delayed loss of firmness and yellowness and inhibited the incidence of lesions caused by Colletotrichum gloeosporioides during the 12 days of storage. Fruits treated with 40 g/L of starch, whether containing prochloraz or not, had unpleasant taste and odor, which suggests the occurrence of fermentation. Control fruits, with and without prochloraz, and those treated with starch with no prochloraz, had nearly 100% lesion occurrence within the 12 days. Starch suspension of 30 g/L, containing prochloraz, was the most effective in maintaining fruit quality.

Morphology and stability of aggregates of an Oxisol according to tillage system and gypsum application

Morphological characterization and aggregate stability is an important factor in evaluating management systems. The aim of this paper is to evaluate the stability and morphology of the aggregates of a dystrophic Oxisol managed with no-tillage and conventional tillage with and without the residual action of gypsum. The experimental design was randomized blocks arranged in split-split plot, where the treatments were two soil management systems (plots) with 0 and 2000 kg ha-1 of gypsum (subplots) and five depths (0-0.05, 0.05-0.10, 0.10-0.15, 0.15-0.20 and 0.20-0.30 m) as the subsubplots, with four replications. The aggregate morphology was determined through images and later evaluated by the Quantporo software. Stability was determined by the wet method. The results showed that the no-tillage system, with or without gypsum residual effect, provided the aggregates with the largest geometric diameters. The combination of no-tillage system and the gypsum residual effect provided rougher aggregates.

Response of rice cultivars to nitrogen in upland conditions

Against the background of a growing world population, rice (Oryza sativa L.) consumption is expected to grow faster than its production. Therefore, an appropriate question would be: how to increase productivity in the short-term? In this respect, it becomes important the implementation of modern agricultural production systems, such as upland rice with supplemental sprinkler irrigation. Additional information is needed to maximize the available resources, with special attention given to research on the use of nitrogen. This study aimed to evaluate the agronomic performance of commercial rice cultivars with different plant characteristics in upland conditions with supplemental sprinkler irrigation, when subjected to nitrogen in topdress application at the R1 stage (panicle differentiation). The experiment was arranged in a randomized block with split plot design, with 65 treatments, consisting of the combination of 13 cultivars in the plots, and five nitrogen levels in the subplots (0, 40, 80, 120 and 160 kg ha-1), with four replications. Genetic variability was detected among rice cultivars and the agronomic performance in response to the applied nitrogen. The topdressing application of nitrogen increases, in general, the production components and grain yield in rice. Cultivars BRS Primavera, Caiapó and IAC 202 stood out for grain yield, followed by Baldo, Carnaroli, BRS Curinga and IAC 500 with lower yields.

Promoting Success in the Introduction of Health Information Systems

The significant number of publications describing unsuccessful cases in the introduction of health information systems makes it advisable to analyze the factors that may be contributing to such failures. However, the very notion of success is not equally assumed in all publications. Based in a literature review, the authors argue that the introduction of systems must be based in an eclectic combination of knowledge fields, adopting methodologies that strengthen the role of organizational culture and human resources in this project, as a whole. On the other hand, the authors argue that the introduction of systems should be oriented by a previously defined matrix of factors, against which the success can be measured.

Silicate fertilizer and irrigation depth in corn production

Calcium-magnesium silicates improve the soil physicochemical properties and provide benefits to plant nutrition, since they are sources of silica, calcium and magnesium. The objective of this study was to evaluate the grain yield of irrigated corn fertilized with calcium-magnesium silicate. The experiment was carried out in a greenhouse in Campina Grande - PB, Brazil, using plastic pots containing 80 kg of soil. The treatments consisted of the combination of four irrigation depths, related to water replacement of 50, 75, 100 and 125% of the crop evapotranspiration, with fertilizer levels of 0, 82, 164 and 246 g of calcium-magnesium silicate, with three replications. The experimental design was in randomized blocks, with the irrigation depths distributed in bands while the silicon levels constituted the subplots. Corn yield was influenced by calcium-magnesium silicate and by irrigation depth, obtaining the greatest grain yield with the dose of 164 g pot-1 irrigated at the highest water level. The water-use efficiency of in corn production tended to decrease when the irrigation depth was increased. The best water-use efficiency was observed when the irrigation level was between 87 and 174 mm, and the dose of silicate was 164 g pot-1.

Action of auxin inhibitors on growth and grain yield of soybean

Soybean genotypes grown in sub-tropical climate may exhibit lodging. The plant lodging is influenced by soil type and fertility level, sowing date, latitude and altitude of the location, plant population and conditions of crop development. Plant regulators and herbicides are able to avoid or reduce plant lodging. This study aimed to verify the effects of the growth regulators TIBA and daminozide on vegetative growth and yield of soybean cultivar CD 214 RR. The experiment was carried out at a field in randomized block design with four replications in a factorial scheme. The A factor was represented by the combination of regulators TIBA and daminozide and its concentrations, and the Factor B was seven times of evaluation of injury and plant height or eight times of evaluation of lodging. In the range of doses used, the application of daminozide resulted in greater injury to soybean plants than TIBA. The smaller plant height was achieved by the application of 6 g ha-1 of TIBA and 1200 g ha-¹ of daminozide. Treatments with daminozide (100 g ha-¹) and TIBA (10 g ha-1) stood out due to the reduced lodging of soybean plants. Grain weight increased linearly when the levels of TIBA increased. There was a negative correlation between lodging and grain yield and a positive correlation between plant height and lodging. There was also a negative correlation between injury caused by the application of plant regulators and lodging.

Tsunami vulnerability assessment of Casablanca-Morocco using numerical modelling and GIS tools

Earthquakes and tsunamis along Morocco's coasts have been reported since historical times. The threat posed by tsunamis must be included in coastal risk studies. This study focuses on the tsunami impact and vulnerability assessment of the Casablanca harbour and surrounding area using a combination of tsunami inundation numerical modelling, field survey data and geographic information system. The tsunami scenario used here is compatible with the 1755 Lisbon event that we considered to be the worst case tsunami scenario. Hydrodynamic modelling was performed with an adapted version of the Cornell Multigrid Coupled Tsunami Model from Cornell University. The simulation covers the eastern domain of the Azores-Gibraltar fracture zone corresponding to the largest tsunamigenic area in the North Atlantic. The proposed vulnerability model attempts to provide an insight into the tsunami vulnerability of building stock. Results in the form of a vulnerability map will be useful for decision makers and local authorities in preventing the community resiliency for tsunami hazards.