Thermal analysis, nuclear magnetic resonance spectroscopy, and impedance spectroscopy of N,N-dimethyl-pyrrolidinium iodide: An ionic solid exhibiting rotator phases

N,N-dimethyl-pyrrolidinium iodide has been investigated using differential scanning calorimetry, nuclear magnetic resonance (NMR) spectroscopy, second moment calculations, and impedance spectroscopy. This pyrrolidinium salt exhibits two solid-solid phase transitions, one at 373 K having an entropy change, Delta S, of 38 J mol(-1) K-1 and one at 478 K having Delta S of 5.7 J mol(-1) K-1. The second moment calculations relate the lower temperature transition to a homogenization of the sample in terms of the mobility of the cations, while the high temperature phase transition is within the temperature region of isotropic tumbling of the cations. At higher temperatures a further decrease in the H-1 NMR linewidth is observed which is suggested to be due to diffusion of the cations. (C) 2005 American Institute of Physics.

Implications of current ecological thinking for biodiversity conservation: A review of the salient issues

Given escalating concern worldwide about the loss of biodiversity, and given biodiversity's centrality to quality of life, it is imperative that current ecological knowledge fully informs societal decision making. Over the past two decades, ecological science has undergone many significant shifts in emphasis and perspective, which have important implications for how we manage ecosystems and species. In particular, a shift has occurred from the equilibrium paradigm to one that recognizes the dynamic, non-equilibrium nature of ecosystems. Revised thinking about the spatial and temporal dynamics of ecological systems has important implications for management. Thus, it is of growing concern to ecologists and others that these recent developments have not been translated into information useful to managers and policy makers. Many conservation policies and plans are still based on equilibrium assumptions. A fundamental difficulty with integrating current ecological thinking into biodiversity policy and management planning is that field observations have yet to provide compelling evidence for many of the relationships suggested by non-equilibrium ecology. Yet despite this scientific uncertainty, management and policy decisions must still be made. This paper was motivated by the need for considered scientific debate on the significance of current ideas in theoretical ecology for biodiversity conservation. This paper aims to provide a platform for such discussion by presenting a critical synthesis of recent ecological literature that (1) identifies core issues in ecological theory, and (2) explores the implications of current ecological thinking for biodiversity conservation.

Seasonal dynamics of a drosophilid (Diptera) assemblage and its potencial as bioindicator in open environments

Drosophila Fallen, 1823 (Diptera, Drosophilidae) is for long a well-established model organism for genetics and evolutionary research. The ecology of these flies, however, has only recently been better studied. Recent papers show that Drosophila assemblies can be used as bioindicators of forested environment degradation. In this work the bioindicator potential of drosophilids was evaluated in a naturally opened environment, a coastal strand-forest (restinga). Data from nine consecutive seasonal collections revealed strong temporal fluctuation pattern of the majority of Drosophila species groups. Drosophila willistoni group was more abundant at autumns, whereas D. cardini and D. tripunctata groups were, respectively, expressive at winters and springs, and D. repleta group at both seasons. The exotic species D. simulans Sturtevant, 1919 (from D. melanogaster group) and Zaprionus indianus Gupta, 1970 were most abundant at summers. Overall, the assemblage structure did not show the same characteristics of forested or urban environments, but was similar to the forests at winters and to cities at summers. This raises the question that this locality may already been under urbanization impact. Also, this can be interpreted as an easily invaded site for exotic species, what might lead to biotic homogenization and therefore can put in check the usage of drosophilid assemblages as bioindicators at open environments.

Interfacial interactions and structure of organic-inorganic nanohybrids

Understanding the interfacial interactions and structure is important to better design and application of organic-inorganic nanohybrids. This paper presents our recent molecular dynamic studies on organoclays and polymer nanocomposites, including the layering behavior of organoclays, structural and dynamic properties of dioctadecyldimethyl ammoniums in organoclays, and interfacial interactions and structure of polyurethane nanocomposites. The results demonstrate that the layering behaviors of organoclays are closely related to the chain length of quaternary alkyl ammoniums and cation exchangeable capacity of clays. In addition to typical layered structures such as monolayer, bilayer and pseudo-trilayer, a pseudo-quadrilayer structure was also observed in organoclays modified with dioctadecyldimethyl ammoniums (DODDMA). In such a structure, alkyl chains do not lie flat within a single layer but interlace, and also jump to the next layer or even the next nearest layer. Moreover, the diffusion constants of nitrogen and methylene atoms increase with the temperature and methelene towards the tail groups. For polyurethane nanocomposite, the van der Waals interaction between apolar alkyl chains and soft segments of polyurethane predominates the interactions between organoclay and polyurethane. Different from most bulk polyurethane systems, there is no distinct phase-separated structure for the polyurethane.

The crystal structure of free human hypoxanthineguanine phosphoribosyltransferase reveals extensive conformational plasticity throughout the catalytic cycle

Human hypoxanthine-guanine phosphoribosyltransferase (HGPRT) catalyses the synthesis of the purine nucleoside monophosphates, IMP and GMP, by the addition of a 6-oxopurine base, either hypoxanthine or guanine, to the 1-beta-position of 5-phospho-U-D-ribosyl-1-pyrophosphate (PRib-PP). The mechanism is sequential, with PRib-PP binding to the free enzyme prior to the base. After the covalent reaction, pyrophosphate is released followed by the nucleoside monophosphate. A number of snapshots of the structure of this enzyme along the reaction pathway have been captured. These include the structure in the presence of the inactive purine base analogue, 7-hydroxy [4,3-d] pyrazolo pyrimidine (HPP) and PRib-PP. Mg2+, and in complex with IMP or GMP. The third structure is that of the immucillinHP.Mg2+.PPi complex, a transition-state analogue. Here, the first crystal structure of free human HGPRT is reported to 1.9 angstrom resolution, showing that significant conformational changes have to occur for the substrate(s) to bind and for catalysis to proceed. Included in these changes are relative movement of subunits within the tetramer, rotation and extension of an active-site alpha-helix (D137-D153), reorientation of key active-site residues K68, D137 and K165, and the rearrangement of three active-site loops (100-128, 165-173 and 186-196). Toxoplasina gondii HGXPRT is the only other 6-oxopurine phosphoribosyltransferase structure solved in the absence of ligands. Comparison of this structure with human HGPRT reveals significant differences in the two active sites, including the structure of the flexible loop containing K68 (human) or K79 (T gondii). (c) 2005 Elsevier Ltd. All rights reserved.

Surface foam film waves studied with high-speed linescan camera

Dynamic foam films have been investigated using an improved experimental set-up with a CCD high-speed linescan camera in conjunction with the Scheludko micro-interferometric cell for studying the drainage and rupture of liquid foam films. The improved experimental set-up increased the sensibility of detection of the local thickness heterogeneities and domains during the film evolution. The evolution of the foam films up to the formation of black spots was recorded in the time intervals of 50ms. The wavelengths of the propagating surface waves and their frequencies were determined experimentally. The experimental results show that the current quasi-static hydrodynamic theory does not properly describe the wave dynamics with inter-domain channels. However, the thermodynamic condition for formation of black spots in the foam films was met by the experimental results. (c) 2005 Elsevier B.V. All rights reserved.

Religions and cultures: Religious dynamics in Latin America

The author seeks to analyse the relationships between religion and culture in Latin America, especially in Brazil, highlighting the fact that the different religions enjoy diverse relationships with culture in a single location. He also addresses the fact that religions interpret culture in different ways and these interpretations help define their conversion strategies and how best to confront opposing religions. For the sake of discussion, the author considers, hypothetically, a not-so-distant future in which Latin America becomes predominantly evangelical, and asks what will happen to Latin America`s supposed Catholic culture if the evangelical religions do indeed take over.

Effect of sodium dodecylbenzene sulfonate on the motion of three-phase contact lines on the Wilhelmy plate surface

The combined approach of the molecular-kinetic and hydrodynamic theories for description of the motion of three-phase gas-liquid-solid contact lines has been examined using the Wilhelmy plate method. The whole dynamic meniscus has been divided into molecular, hydrodynamic, and static-like regions. The Young-Laplace equation and the molecular-kinetic and hydrodynamic dewetting theories have been applied to describe the meniscus profiles and contact angle. The dissipative forces accompanying the dynamic dewetting have also been investigated. The experiments with a Wilhelmy plate made from an acrylic polymer sheet were carried out using a computerized apparatus for contact angle analysis (OCA 20, DataPhysics, Germany). The extrapolated dynamic contact angle versus velocity of the three-phase contact line for Milli-Q water and 5 x 10(-4) M SDBS solution was experimentally obtained and compared with the combined MHD models with low and moderate Reynolds numbers. The models predict similar results for the extrapolated contact angle. SDBS decreases the equilibrium contact angle and increases the molecular jumping length but does not affect the molecular frequency significantly. The hydrodynamic deformation of the meniscus, viscous dissipation, and friction were also influenced by the SDBS surfactant. (c) 2005 Elsevier Inc. All rights reserved.

Eutectic modification and microstructure development in Al-Si alloys

Recent increasing applications for cast Al-Si alloys are particularly driven by the need for lightweighting components in the automotive sector. To improve mechanical properties, elements such as strontium, sodium and antimony can be added to modify the eutectic silicon from coarse and plate-like to fine and fibrous morphology. It is only recently being noticed that the morphological transformation resulting from eutectic modification is also accompanied by other, equally significant, but often unexpected changes. These changes can include a 10-fold increase in the eutectic grain size, redistribution of low-melting point phases and porosity as well as surface finish, consequently leading to variations in casting quality. This paper shows the state-of-the-art in understanding the mechanism of eutectic nucleation and growth in Al-Si alloys, inspecting samples, both quenched and uninterrupted, on the macro, micro and nano-scale. It shows that significant variations in eutectic nucleation and growth dynamics occur in AI-Si alloys as a function of the type and amount of modifier elements added. The key role of AIP particles in nucleating silicon is demonstrated. (c) 2005 Elsevier B.V. All rights reserved.

Semiquantum versus semiclassical mechanics for simple nonlinear systems

Quantum mechanics has been formulated in phase space, with the Wigner function as the representative of the quantum density operator, and classical mechanics has been formulated in Hilbert space, with the Groenewold operator as the representative of the classical Liouville density function. Semiclassical approximations to the quantum evolution of the Wigner function have been defined, enabling the quantum evolution to be approached from a classical starting point. Now analogous semiquantum approximations to the classical evolution of the Groenewold operator are defined, enabling the classical evolution to be approached from a quantum starting point. Simple nonlinear systems with one degree of freedom are considered, whose Hamiltonians are polynomials in the Hamiltonian of the simple harmonic oscillator. The behavior of expectation values of simple observables and of eigenvalues of the Groenewold operator are calculated numerically and compared for the various semiclassical and semiquantum approximations.

Driving mechanisms for groundwater flow and salt transport in a subterranean estuary

This paper presents field measurements and numerical simulations of groundwater dynamics in the intertidal zone of a sandy meso-tidal beach. The study, focusing on vertical hydraulic gradients and pore water salinities, reveals that tides and waves provide important forcing mechanisms for flow and salt transport in the nearshore aquifer. Such forcing, interacting with the beach morphology, enhances the exchange between the aquifer and ocean. The spatial and temporal variations of vertical hydraulic gradients demonstrate the complexity and dynamic nature of the processes and the extent of mixing between fresh groundwater and seawater in a subterranean estuary''. These results provide evidence of a potentially important reaction zone in the nearshore aquifer driven by oceanic oscillations. Land-derived contaminants may undergo important biogeochemical transformations in this zone prior to discharge.

Tidal influence on behaviour of a coastal aquifer adjacent to a low-relief estuary

The tidal influence on groundwater hydrodynamics, salt-water intrusion and submarine groundwater discharge from coastal/estuarine aquifers is poorly quantified for systems with a mildly sloping beach, in contrast to the case where a vertical beach face is assumed. We investigated the effect of beach slope for a coastal aquifer adjacent to a low-relief estuary, where industrial waste was emplaced over the aquifer. The waste was suspected to discharge leachate towards the estuary. Field observations at various locations showed that tidally induced groundwater head fluctuations were skewed temporally. Frequency analysis suggested that the fluctuation amplitudes decreased exponentially and the phase-tags increased Linearly for the primary tidal signals as they propagated inland. Salinisation zones were observed in the bottom part of the estuary and near the beach surface. Flow and transport processes in a cross-section perpendicular to the estuary were simulated using SEAWAT-2000, which is capable of depicting density-dependent flow and multi-species transport. The simulations showed that the modelled water table fluctuations were in good agreement with the monitored data. Further simulations were conducted to gain insight into the effects of beach slope. In particular the limiting case of a vertical beach face was considered. The simulations showed that density difference and tidal forcing drive a more complex hydrodynamic pattern for the mildly sloping beach than the vertical beach, as well as a profound asymmetry in tidally induced water table fluctuations and enhanced salt-water intrusion. The simulation results also indicated that contaminant transport from the aquifer to the estuary was affected by the tide, where for the mildly sloping beach, the tide tended to intensify the vertical mass exchange in the vicinity of the shorelines, (c) 2005 Elsevier B.V. All rights reserved.

Diel vertical migration: Modelling light-mediated mechanisms

Light is generally regarded as the most likely cue used by zooplankton to regulate their vertical movements through the water column. However, the way in which light is used by zooplankton as a cue is not well understood. In this paper we present a mathematical model of diel vertical migration which produces vertical distributions of zooplankton that vary in space and time. The model is used to predict the patterns of vertical distribution which result when animals are assumed to adopt one of three commonly proposed mechanisms for vertical swimming. First, we assume zooplankton tend to swim towards a preferred intensity of light. We then assume zooplankton swim in response to either the rate of change in light intensity or the relative rate of change in light intensity. The model predicts that for all three mechanisms movement is fastest at sunset and sunrise and populations are primarily influenced by eddy diffusion at night in the absence of a light stimulus. Daytime patterns of vertical distribution differ between the three mechanisms and the reasons for the predicted differences are discussed. Swimming responses to properties of the light field are shown to be adequate for describing diel vertical migration where animals congregate in near surface waters during the evening and reside at deeper depths during the day. However, the model is unable to explain how some populations halt their ascent before reaching surface waters or how populations re-congregate in surface waters a few hours before sunrise, a phenomenon which is sometimes observed in the held. The model results indicate that other exogenous or endogenous factors besides light may play important roles in regulating vertical movement.

Analysis of dynamic process models for structural insight and model reduction .1. Structural identification measures

An important consideration in the development of mathematical models for dynamic simulation, is the identification of the appropriate mathematical structure. By building models with an efficient structure which is devoid of redundancy, it is possible to create simple, accurate and functional models. This leads not only to efficient simulation, but to a deeper understanding of the important dynamic relationships within the process. In this paper, a method is proposed for systematic model development for startup and shutdown simulation which is based on the identification of the essential process structure. The key tool in this analysis is the method of nonlinear perturbations for structural identification and model reduction. Starting from a detailed mathematical process description both singular and regular structural perturbations are detected. These techniques are then used to give insight into the system structure and where appropriate to eliminate superfluous model equations or reduce them to other forms. This process retains the ability to interpret the reduced order model in terms of the physico-chemical phenomena. Using this model reduction technique it is possible to attribute observable dynamics to particular unit operations within the process. This relationship then highlights the unit operations which must be accurately modelled in order to develop a robust plant model. The technique generates detailed insight into the dynamic structure of the models providing a basis for system re-design and dynamic analysis. The technique is illustrated on the modelling for an evaporator startup. Copyright (C) 1996 Elsevier Science Ltd

Analysis of dynamic models for structural insight and model reduction .2. A multi-stage compressor shutdown case-study

In this second paper, the three structural measures which have been developed are used in the modelling of a three stage centrifugal synthesis gas compressor. The goal of this case study is to determine the essential mathematical structure which must be incorporated into the compressor model to accurately model the shutdown of this system. A simple, accurate and functional model of the system is created via three structural measures. It was found that the model can be correctly reduced into its basic modes and that the order of the differential system can be reduced from 51(st) to 20(th). Of the 31 differential equational 21 reduce to algebraic relations, 8 become constants and 2 can be deleted thereby increasing the algebraic set from 70 to 91 equations. An interpretation is also obtained as to which physical phenomena are dominating the dynamics of the compressor add whether the compressor will enter surge during the shutdown. Comparisons of the reduced model performance against the full model are given, showing the accuracy and applicability of the approach. Copyright (C) 1996 Elsevier Science Ltd