Effect of CO2 exposure on free volumes in polystyrene studied by positron annihilation spectroscopy

Free‐volume properties, size and distribution, in amorphous polystyrene exposed to CO₂ gases have been measured as a function of pressure to 800 psi (5.5 MPa), of time, and of temperature using positron annihilation lifetime spectroscopy. The free volume increases significantly and its distribution broadens as a function of pressure. The free volume relaxes as a function of time with a characteristic time of 15 h, and 5.7 h for 400, and 800 psi, respectively, after depressurizing under vacuum. A portion of free volume created by CO₂ exposure remains permanently in the polymer after CO₂ exposure. The glass transition temperature decreases significantly as a function of CO₂ pressure from the free‐volume data and is compared with the differential scanning calorimeter results. The observed free‐volume variations as a function of pressure, time, and temperature are discussed in terms of hole expansion, creation, free‐volume relaxation, plasticization, and hole filling in amorphous polymers. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 388–405, 2008     

Geometric criteria for the nonexistence of cycles in Gause-type predator-prey systems

The global stability of a multi-species interacting system has apparently important biological implications. In this paper we study the global stability of Gause-type predator-prey models by providing new criteria for the nonexistence of cycles and limit cycles. Our criteria have clear geometrical interpretations and are easier to apply than other methods employed in recent studies. Using these criteria and related techniques we are able to develop new results on the existence and uniqueness of cycles in Gause-type models with various growth and response functions.

     

Viscosity of n-alkyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)amide ionic liquids saturated with compressed CO2

The viscosity of imidazolium-based ionic liquids (ILs) saturated with gaseous, liquid and supercritical carbon dioxide (CO₂) was measured by a high-pressure viscometer at three different temperatures (25, 50, and 70 °C). The high-pressure viscosity of 1-ethyl-3-methylimidazolium ([EMIm]), 1-n-hexyl-3-methylimidazolium ([HMIm]), and 1-n-decyl-3-methylimidazolium ([DMIm]) cations with a common anion, bis(trifluoromethylsulfonyl)amide ([Tf₂N]), saturated with CO₂ was measured up to a maximum of 287 bar. As CO₂ pressure is increased the viscosity of the IL mixture dramatically decreases. While, the ambient pressure viscosity of 1-alkyl-3-methyl-imidazolium [Tf₂N] ILs increases significantly with increasing chain length, the viscosity of all the CO₂-saturated ILs becomes very similar at high CO₂ pressures. From previous vapor–liquid equilibrium data, the viscosity with concentration was determined and found to be the primary factor to describe the fractional viscosity reduction. Several predictive and correlative methods were investigated for the mixture viscosity given pure component properties and include arithmetic mixing rules, the Irving (Predictive Arrhenius) model, Grunberg equation, etc. The modified Grunberg model with one adjustable parameter provided an adequate fit to the data.     

Calculating singular integrals as an ill-posed problem

Summary Applying numerical quadrature to singular integrals in a straightforward way leads to uncontrolled instability with respect to data errors. In this paper we describe how to control this instability.Dedicated to Professor G. Hämmerlin on the occasion of his 60th birthday.     

Temperament Development Modeled as a Nonlinear Complex Adaptive System

Using approach-withdrawal (AW) as a specific instance of temperament, a theoretical model of temperament as a complex dynamic system is proposed. Developmental contextualism (Lerner, 1998) serves as a guiding theory in determining the structural components of the system and Kauffman's (1993) Boolean models of self-organization are adapted to estimate the parameter functions. In this model P(AW) = f(, ) where P(AW) is the probability density function of an approach or a withdrawal response, ( is a standardized parameter estimate of the biological sensitivity to stimulation, and is a standardized parameter estimate of the contextual response to an approach or withdrawal response. It is theorized that the functions of ( and follow a Hill function of the forms: d /dt = (²/c² + ²) – K₁ d /dt = ( ²/c² + ²) – K₂, where K₁, K₂, and c are system constants. This results in a double sigmoid function in which at extreme values of and the system stabilizes on a steady state of either approach or withdrawal response patterns. At intermediate parameter values the probability density functions of approach and withdrawal responses are wider. Thus, AW can be modeled as representing two basins of attraction. In addition, considerations are given to the systems sensitivity to initial conditions.     

Impact of M1A1 main battle tank disturbance on soil quality, invertebrates, and vegetation characteristics

Military training commonly results in land degradation, but protocols for assessing and predicting long-term environmental impact are lacking. An ability to assess the impact of repeated disturbance and subsequent recovery is needed to balance training requirements against environmental quality. To develop methodology for assessing soil quality, a study evaluating disturbance resulting from tank maneuvers was initiated on Fort Riley Military Installation, Kansas. The objectives were to identify and quantify soil-quality indicators on two soil types exposed to controlled tank traffic. We examined physical, chemical, and biotic indicators after treatments were applied during wet and dry soil conditions. A randomized complete-block design, with three blocks per soil type and three treatments per block, was used. Treatments consisted of disturbance created by a 63-ton M1A1 tank making five passes in a figure-8 pattern during either dry or wet soil conditions. The M1A1 was operated at a speed of approximately 8 km/h. Control plots received no tank traffic. Soil-quality indicators evaluated were soil compaction, soil penetration resistance, rut depth, soil bulk density, soil texture, soil chemical composition, plant biomass, soil microbial diversity, and nematode and earthworm taxa. Soil-quality indicators were sampled within one week after tank disturbance. Preliminary data indicate soil-texture-dependent treatment effects (p  0.05) for bulk density and porosity. Bulk density increased and porosity decreased on trafficked areas, in the silt loam soil, but showed no change in the silty clay loam soil. Disturbance during wet soil conditions raised penetrometer resistance and gravimetric water content more than disturbance during dry soil conditions (p  0.05). A significant difference in disturbance was measured between the outside and inside portion of the same track (p  0.01 and 0.001, respectively). The outside track caused the greatest amount of disturbance, as measured by the height of the disturbed soil ridge above the track bed. Tank disturbance significantly reduced total vegetative biomass (p  0.05) compared with that of un-trafficked areas. Disturbance under wet soil conditions significantly reduced grass biomass (p = 0.040), whereas disturbance under dry soil conditions significantly reduced forb biomass (p = 0.0247) compared to un-trafficked areas. Total earthworm abundance (p = 0.011) was reduced by 82% when disturbance occurred during wet soil conditions regardless of soil type.     

Application of quasilinearization technique to the vertical channel flow and heat convection

The quasilinearization technique, also known as the generalized Newton-Raphson method, is employed to solve the problem of fluid injection through one side of a long vertical channel. With very approximate starting values, only a few iterations are needed to obtain a result with high accuracy. The results are compared with those obtained by the perturbation technique. Although the perturbation technique is perhaps the simplest and the most straight-forward method to achieve solutions to non-linear boundary value problems, the limitation on the magnitude of perturbed parameters hinders its applicability.     

Modeling study of non-line-narrowed hole-burned spectra in weakly coupled dimers and multi-chromophoric molecular assemblies

Several different models have been proposed to explain the origin of the complex anti-hole features observed in hole-burned (HB) spectra of excitonically coupled systems such as photosynthetic complexes. This lack of consensus presents a serious constraint on the interpretation of HB spectra and the underlying electronic structures of these systems. To resolve this problem we present results of modeling studies of non-resonant HB spectra taking uncorrelated excitation energy transfer and excitonic interactions into account. Simplified analytical results are compared with Monte Carlo simulations in which excitonic interactions are explicitly taken into account in order to disentangle a number of distinct effects. It is shown that these effects can accurately account for both hole shapes and the broad anti-hole structure observed in excitonically coupled systems. We argue that these models will provide a necessary framework for probing the electronic structure of these systems via HB spectroscopy.     

Design, synthesis, and in vitro evaluation of potential West Nile virus protease inhibitors based on the 1-oxo-1,2,3,4-tetrahydroisoquinoline and 1-oxo-1,2-dihydroisoquinoline scaffolds

The 1-oxo-1, 2, 3, 4-tetrahydroisoquinoline and 1-Oxo-1, 2-dihydroisoquinoline scaffolds were utilized in the design and solution phase synthesis of focused libraries of compounds for screening against West Nile Virus (WNV) protease. Exploratory studies have led to the identification of a WNV protease inhibitor (a 1-oxo-1, 2-dihydroisoquinoline-based derivative, 12j) which could potentially serve as a launching pad for a hit-to-lead optimization campaign. The identified hit was devoid of any inhibitory activity toward a panel of mammalian serine proteases.