Direct detection of dimethylstannylene and tetramethyldistannene in solution and the gas phase by laser flash photolysis of 1,1-dimethylstannacyclopent-3-enes

The photochemistry of 1,1-dimethyl- and 1,1,3,4-tetramethylstannacyclopent-3-ene (4a and 4b,respectively) has been studied in the gas phase and in hexane solution by steady-state and 193-nm laser flash photolysis methods. Photolysis of the two compounds results in the formation of 1,3-butadiene (from 4a) and 2,3-dimethyl-1,3-butadiene (from 4b) as the major products, suggesting that cycloreversion to yield dimethylstannylene (SnMe2) is the main photodecomposition pathway of these molecules. Indeed, the stannylene has been trapped as the Sn-H insertion product upon photolysis of 4a in hexane containing trimethylstannane. Flash photolysis of 4a in the gas phase affords a transient absorbing in the 450-520nm range that is assigned to SnMe2 by comparison of its spectrum and reactivity to those previously reported from other precursors. Flash photolysis of 4b in hexane solution affords results consistent with the initial formation of SnMe2 (lambda(max) approximate to 500 nm), which decays over similar to 10 mu s to form tetramethyldistannene (5b; lambda(max) approximate to 470 nm). The distannene decays over the next ca. 50 mu s to form at least two other longer-lived species, which are assigned to higher SnMe2 oligomers. Time-dependent DFT calculations support the spectral assignments for SnMe2 and Sn2Me4, and calculations examining the variation in bond dissociation energy with substituent (H, Me, and Ph) in disilenes, digermenes, and distannenes rule out the possibility that dimerization of SnMe2 proceeds reversibly. Addition of methanol leads to reversible reaction with SnMe2 to form a transient absorbing at lambda(max) approximate to 360 nm, which is assigned to the Lewis acid-base complex between SnMe2 and the alcohol.

What have we learnt about heavy carbenes through laser flash photolysis studies?

Time resolved gas-phase kinetic studies have contributed a great deal of fundamental information about the reactions and reactivity of heavy carbenes (silylenes, germylenes and stannylenes) during the past two decades. In this article we trace the development of our understanding through the mechanistic themes of intermediate complexes, third body assisted associations, catalysed reactions, non-observed reactions and substituent effects. Ab initio (quantum chemical) calculations have substantially assisted mechanistic interpretation and are discussed where appropriate. Trends in reactivity are identified and some signposts to future studies are indicated. This review, although detailed, is not comprehensive.

Integration of remote sensing and GIS for modelling flash floods in Wadi Hudain catchment, Egypt

This paper presents a new approach to modelling flash floods in dryland catchments by integrating remote sensing and digital elevation model (DEM) data in a geographical information system (GIS). The spectral reflectance of channels affected by recent flash floods exhibit a marked increase, due to the deposition of fine sediments in these channels as the flood recedes. This allows the parts of a catchment that have been affected by a recent flood event to be discriminated from unaffected parts, using a time series of Landsat images. Using images of the Wadi Hudain catchment in southern Egypt, the hillslope areas contributing flow were inferred for different flood events. The SRTM3 DEM was used to derive flow direction, flow length, active channel cross-sectional areas and slope. The Manning Equation was used to estimate the channel flow velocities, and hence the time-area zones of the catchment. A channel reach that was active during a 1985 runoff event, that does not receive any tributary flow, was used to estimate a transmission loss rate of 7·5 mm h−1, given the maximum peak discharge estimate. Runoff patterns resulting from different flood events are quite variable; however the southern part of the catchment appears to have experienced more floods during the period of study (1984–2000), perhaps because the bedrock hillslopes in this area are more effective at runoff production than other parts of the catchment which are underlain by unconsolidated Quaternary sands and gravels. Due to high transmission loss, runoff generated within the upper reaches is rarely delivered to the alluvial fan and Shalateen city situated at the catchment outlet. The synthetic GIS-based time area zones, on their own, cannot be relied on to model the hydrographs reliably; physical parameters, such as rainfall intensity, distribution, and transmission loss, must also be considered.

The 20 February 2010 Madeira flash-floods: synoptic analysis and extreme rainfall assessment

This study aims to characterise the rainfall exceptionality and the meteorological context of the 20 February 2010 flash-floods in Madeira (Portugal). Daily and hourly precipitation records from the available rain-gauge station networks are evaluated in order to reconstitute the temporal evolution of the rainstorm, as its geographic incidence, contributing to understand the flash-flood dynamics and the type and spatial distribution of the associated impacts. The exceptionality of the rainstorm is further confirmed by the return period associated with the daily precipitation registered at the two long-term record stations, with 146.9 mm observed in the city of Funchal and 333.8 mm on the mountain top, corresponding to an estimated return period of approximately 290 yr and 90 yr, respectively. Furthermore, the synoptic associated situation responsible for the flash-floods is analysed using different sources of information, e.g., weather charts, reanalysis data, Meteosat images and radiosounding data, with the focus on two main issues: (1) the dynamical conditions that promoted such anomalous humidity availability over the Madeira region on 20 February 2010 and (2) the uplift mechanism that induced deep convection activity.

The catastrophic flash-flood event of 8–9 September 2002 in the Gard region, France: a first case study for the Cévennes–Vivarais Mediterranean Hydrometeorological Observatory

The Cévennes–Vivarais Mediterranean Hydrometeorological Observatory (OHM-CV) is a research initiative aimed at improving the understanding and modeling of the Mediterranean intense rain events that frequently result in devastating flash floods in southern France. A primary objective is to bring together the skills of meteorologists and hydrologists, modelers and instrumentalists, researchers and practitioners, to cope with these rather unpredictable events. In line with previously published flash-flood monographs, the present paper aims at documenting the 8–9 September 2002 catastrophic event, which resulted in 24 casualties and an economic damage evaluated at 1.2 billion euros (i.e., about 1 billion U.S. dollars) in the Gard region, France. A description of the synoptic meteorological situation is first given and shows that no particular precursor indicated the imminence of such an extreme event. Then, radar and rain gauge analyses are used to assess the magnitude of the rain event, which was particularly remarkable for its spatial extent with rain amounts greater than 200 mm in 24 h over 5500 km2. The maximum values of 600–700 mm observed locally are among the highest daily records in the region. The preliminary results of the postevent hydrological investigation show that the hydrologic response of the upstream watersheds of the Gard and Vidourle Rivers is consistent with the marked space–time structure of the rain event. It is noteworthy that peak specific discharges were very high over most of the affected areas (5–10 m3 s−1 km−2) and reached locally extraordinary values of more than 20 m3 s−1 km−2. A preliminary analysis indicates contrasting hydrological behaviors that seem to be related to geomorphological factors, notably the influence of karst in part of the region. An overview of the ongoing meteorological and hydrological research projects devoted to this case study within the OHM-CV is finally presented.

Calibration of structure in a distributed forecasting model for a semiarid flash flood: dynamic surface storage and channel roughness

Flash floods pose a significant danger for life and property. Unfortunately, in arid and semiarid environment the runoff generation shows a complex non-linear behavior with a strong spatial and temporal non-uniformity. As a result, the predictions made by physically-based simulations in semiarid areas are subject to great uncertainty, and a failure in the predictive behavior of existing models is common. Thus better descriptions of physical processes at the watershed scale need to be incorporated into the hydrological model structures. For example, terrain relief has been systematically considered static in flood modelling at the watershed scale. Here, we show that the integrated effect of small distributed relief variations originated through concurrent hydrological processes within a storm event was significant on the watershed scale hydrograph. We model these observations by introducing dynamic formulations of two relief-related parameters at diverse scales: maximum depression storage, and roughness coefficient in channels. In the final (a posteriori) model structure these parameters are allowed to be both time-constant or time-varying. The case under study is a convective storm in a semiarid Mediterranean watershed with ephemeral channels and high agricultural pressures (the Rambla del Albujón watershed; 556 km 2 ), which showed a complex multi-peak response. First, to obtain quasi-sensible simulations in the (a priori) model with time-constant relief-related parameters, a spatially distributed parameterization was strictly required. Second, a generalized likelihood uncertainty estimation (GLUE) inference applied to the improved model structure, and conditioned to observed nested hydrographs, showed that accounting for dynamic relief-related parameters led to improved simulations. The discussion is finally broadened by considering the use of the calibrated model both to analyze the sensitivity of the watershed to storm motion and to attempt the flood forecasting of a stratiform event with highly different behavior.

How do people perceive, understand, and anticipate responding to flash flood risks and warnings? Results from a public survey in Boulder, Colorado, USA

This study investigates flash flood forecast and warning communication, interpretation, and decision making, using data from a survey of 418 members of the public in Boulder, Colorado, USA. Respondents to the public survey varied in their perceptions and understandings of flash flood risks in Boulder, and some had misconceptions about flash flood risks, such as the safety of crossing fast-flowing water. About 6% of respondents indicated consistent reversals of US watch-warning alert terminology. However, more in-depth analysis illustrates the multi-dimensional, situationally dependent meanings of flash flood alerts, as well as the importance of evaluating interpretation and use of warning information along with alert terminology. Some public respondents estimated low likelihoods of flash flooding given a flash flood warning; these were associated with lower anticipated likelihood of taking protective action given a warning. Protective action intentions were also lower among respondents who had less trust in flash flood warnings, those who had not made prior preparations for flash flooding, and those who believed themselves to be safer from flash flooding. Additional analysis, using open-ended survey questions about responses to warnings, elucidates the complex, contextual nature of protective decision making during flash flood threats. These findings suggest that warnings can play an important role not only by notifying people that there is a threat and helping motivate people to take protective action, but also by helping people evaluate what actions to take given their situation.

A psychophysical and computational analysis of the spatio-temporal mechanisms underlying the flash-lag effect

Several accounts put forth to explain the flash-lag effect (FLE) rely mainly on either spatial or temporal mechanisms. Here we investigated the relationship between these mechanisms by psychophysical and theoretical approaches. In a first experiment we assessed the magnitudes of the FLE and temporal-order judgments performed under identical visual stimulation. The results were interpreted by means of simulations of an artificial neural network, that wits also employed to make predictions concerning the F LE. The model predicted that a spatio-temporal mislocalisation would emerge from two, continuous and abrupt-onset, moving stimuli. Additionally, a straightforward prediction of the model revealed that the magnitude of this mislocalisation should be task-dependent, increasing when the use of the abrupt-onset moving stimulus switches from a temporal marker only to both temporal and spatial markers. Our findings confirmed the model`s predictions and point to an indissoluble interplay between spatial facilitation and processing delays in the FLE.

Improved Prediction of Hydrocarbon Flash Points from Boiling Point Data

Flash points (T(FP)) of hydrocarbons are calculated from their flash point numbers, N(FP), with the relationship T(FP) (K) = 23.369N(FP)(2/3) + 20.010N(FP)(1/3) + 31.901 In turn, the N(FP) values can be predicted from experimental boiling point numbers (Y(BP)) and molecular structure with the equation N(FP) = 0.987 Y(BP) + 0.176D + 0.687T + 0.712B - 0.176 where D is the number of olefinic double bonds in the structure, T is the number of triple bonds, and B is the number of aromatic rings. For a data set consisting of 300 diverse hydrocarbons, the average absolute deviation between the literature and predicted flash points was 2.9 K.

Calculating Flash Point Numbers from Molecular Structure: An Improved Method for Predicting the Flash Points of Acyclic Alkanes

We report a novel method for calculating flash points of acyclic alkanes from flash point numbers, N(FP), which can be calculated from experimental or calculated boiling point numbers (Y(BP)) with the equation N(FP) = 1.020Y(BP) - 1.083 Flash points (FP) are then determined from the relationship FP(K) = 23.369N(FP)(2/3) + 20.010N(FP)(1/3) + 31.901 For it data set of 102 linear and branched alkanes, the correlation of literature and predicted flash points has R(2) = 0.985 and an average absolute deviation of 3.38 K. N(FP) values can also be estimated directly from molecular structure to produce an even closer correspondence of literature and predicted FP values. Furthermore, N(FP) values provide a new method to evaluate the reliability of literature flash point data.

Simple Method to Evaluate and to Predict Flash Points of Organic Compounds

Flash points (T(FP)) of organic compounds are calculated from their flash point numbers, N(FP), with the relationship T(FP) = 23.369N(FP)(2/3) + 20.010N(FP)(1/3) + 31.901. In turn, the N(FP) values can be predicted from boiling point numbers (Y(BP)) and functional group counts with the equation N(FP) = 0.974Y(BP) + Sigma(i)n(i)G(i) + 0.095 where G(i) is a functional group-specific contribution to the value of N(FP) and n(i) is the number of such functional groups in the structure. For a data set consisting of 1000 diverse organic compounds, the average absolute deviation between reported and predicted flash points was less than 2.5 K.

Interfacial Electron Transfer Dynamics Following Laser Flash Photolysis of [Ru(bpy)(2)((4,4 `-PO(3)H(2))(2)bpy)](2+) in TiO(2) Nanoparticle Films in Aqueous Environments

Nanosecond laser flash photolysis has been used to investigate injection and back electron transfer from the complex [(Ru-(bpy)(2)(4,4`-(PO(3)H(2))(2)bpy)](2+) surface-bound to TiO(2) (TiO(2)-Ru(II)). The measurements were conducted under conditions appropriate for water oxidation catalysis by known single-site water oxidation catalysts. Systematic variations in average lifetimes for back electron transfer, - were observed with changes in pH, surface coverage, incident excitation intensity, and applied bias. The results were qualitatively consistent with a model involving rate-limiting thermal activation of injected electrons from trap sites to the conduction band or shallow trap sites followed by site-to-site hopping and interfacial electron transfer, TiO(2)(e(-))-Ru(3+) -> TiO(2)-Ru(2+). The appearance of pH-dependent decreases in the efficiency of formation of TiO(2)-Ru(3+) and in incident-photon-to-current efficiencies with the added reductive scavenger hydroquinone point to pH-dependent back electron transfer processes on both the sub-nanosecond and millisecond-microsecond time scales, which could be significant in limiting long-term storage of multiple redox equivalents.

Facebook3d

INTRODUCTION With the advent of Web 2.0, social networking websites like Facebook, MySpace and LinkedIn have become hugely popular. According to (Nilsen, 2009), social networking websites have global1 figures of almost 250 millions unique users among the top five2, with the time people spend on those networks increasing 63% between 2007 and 2008. Facebook alone saw a massive growth of 566% in number of minutes in the same period of time. Furthermore their appeal is clear, they enable users to easily form persistent networks of friends with whom they can interact and share content. Users then use those networks to keep in touch with their current friends and to reconnect with old friends. However, online social network services have rapidly evolved into highly complex systems which contain a large amount of personally salient information derived from large networks of friends. Since that information varies from simple links to music, photos and videos, users not only have to deal with the huge amount of data generated by them and their friends but also with the fact that it‟s composed of many different media forms. Users are presented with increasing challenges, especially as the number of friends on Facebook rises. An example of a problem is when a user performs a simple task like finding a specific friend in a group of 100 or more friends. In that case he would most likely have to go through several pages and make several clicks till he finds the one he is looking for. Another example is a user with more than 100 friends in which his friends make a status update or another action per day, resulting in 10 updates per hour to keep up. That is plausible, especially since the change in direction of Facebook to rival with Twitter, by encouraging users to update their status as they do on Twitter. As a result, to better present the web of information connected to a user the use of better visualizations is essential. The visualizations used nowadays on social networking sites haven‟t gone through major changes during their lifetimes. They have added more functionality and gave more tools to their users, but still the core of their visualization hasn‟t changed. The information is still presented in a flat way in lists/groups of text and images which can‟t show the extra connections pieces of information. Those extra connections can give new meaning and insights to the user, allowing him to more easily see if that content is important to him and the information related to it. However showing extra connections of information but still allowing the user to easily navigate through it and get the needed information with a quick glance is difficult. The use of color coding, clusters and shapes becomes then essential to attain that objective. But taking into consideration the advances in computer hardware in the last decade and the software platforms available today, there is the opportunity to take advantage of 3D. That opportunity comes in because we are at a phase were the hardware and the software available is ready for the use of 3D in the web. With the use of the extra dimension brought by 3D, visualizations can be constructed to show the content and its related information to the user at the same screen and in a clear way. Also it would allow a great deal of interactivity. Another opportunity to create better information‟s visualization presents itself in the form of the open APIs, specifically the ones made available by the social networking sites. Those APIs allow any developers to create their own applications or sites taking advantage of the huge amount of information there is on those networks. Specifically to this case, they open the door for the creation of new social network visualizations. Nevertheless, the third dimension is by itself not enough to create a better interface for a social networking website, there are some challenges to overcome. One of those challenges is to make the user understand what the system is doing during the interaction with the user. Even though that is important in 2D visualizations, it becomes essential in 3D due to the extra dimension. To overcome that challenge it‟s necessary the use of the principles of animations defined by the artists at Walt Disney Studios (Johnston, et al., 1995). By applying those principles in the development of the interface, the actions of the system in response to the user inputs became clear and understandable. Furthermore, a user study needs to be performed so the users‟ main goals and motivations, while navigating the social network, are revealed. Their goals and motivations are important in the construction of an interface that reflects the user expectations for the interface, but also helps in the development of appropriate metaphors. Those metaphors have an important role in the interface, because if correctly chosen they help the user understand the elements of the interface instead of making him memorize it. The last challenge is the use of 3D visualization on the web, since there have been several attempts to bring 3D into it, mainly with the various versions of VRML which were destined to failure due to the hardware limitations at the time. However, in the last couple of years there has been a movement to make the necessary tools to finally allow developers to use 3D in a useful way, using X3D or OpenGL but especially flash. This thesis argues that there is a need for a better social network visualization that shows all the dimensions of the information connected to the user and that allows him to move through it. But there are several characteristics the new visualization has to possess in order for it to present a real gain in usability to Facebook‟s users. The first quality is to have the friends at the core of its design, and the second to make use of the metaphor of circles of friends to separate users in groups taking into consideration the order of friendship. To achieve that several methods have to be used, from the use of 3D to get an extra dimension for presenting relevant information, to the use of direct manipulation to make the interface comprehensible, predictable and controllable. Moreover animation has to be use to make all the action on the screen perceptible to the user. Additionally, with the opportunity given by the 3D enabled hardware, the flash platform, through the use of the flash engine Papervision3D and the Facebook platform, all is in place to make the visualization possible. But even though it‟s all in place, there are challenges to overcome like making the system actions in 3D understandable to the user and creating correct metaphors that would allow the user to understand the information and options available to him. This thesis document is divided in six chapters, with Chapter 2 reviewing the literature relevant to the work described in this thesis. In Chapter 3 the design stage that resulted in the application presented in this thesis is described. In Chapter 4, the development stage, describing the architecture and the components that compose the application. In Chapter 5 the usability test process is explained and the results obtained through it are presented and analyzed. To finish, Chapter 6 presents the conclusions that were arrived in this thesis.