Gas-phase reactions of aryl radicals with 2-butyne : an experimental and theoretical investigation employing the N-methyl-pyridinium-4-yl radical cation

Aromatic radicals form in a variety of reacting gas-phase systems, where their molecular weight growth reactions with unsaturated hydrocarbons are of considerable importance. We have investigated the ion-molecule reaction of the aromatic distonic N-methyl-pyridinium-4-yl (NMP) radical cation with 2-butyne (CH3C CCH3) using ion trap mass spectrometry. Comparison is made to high-level ab initio energy surfaces for the reaction of NMP and for the neutral phenyl radical system. The NMP radical cation reacts rapidly with 2-butyne at ambient temperature, due to the apparent absence of any barrier. The activated vinyl radical adduct predominantly dissociates via loss of a H atom, with lesser amounts of CH3 loss. High-resolution Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry allows us to identify small quantities of the collisionally deactivated reaction adduct. Statistical reaction rate theory calculations (master equation/RRKM theory) on the NMP + 2-butyne system support our experimental findings, and indicate a mechanism that predominantly involves an allylic resonance-stabilized radical formed via H atom shuttling between the aromatic ring and the C-4 side-chain, followed by cyclization and/or low-energy H atom beta-scission reactions. A similar mechanism is demonstrated for the neutral phenyl radical (Ph center dot)+2-butyne reaction, forming products that include 3-methylindene. The collisionally deactivated reaction adduct is predicted to be quenched in the form of a resonance-stabilized methylphenylallyl radical. Experiments using a 2,5-dichloro substituted methyl-pyridiniumyl radical cation revealed that in this case CH3 loss from the 2-butyne adduct is favoured over H atom loss, verifying the key role of ortho H atoms, and the shuttling mechanism, in the reactions of aromatic radicals with alkynes. As well as being useful phenyl radical analogues, pyridiniumyl radical cations may form in the ionosphere of Titan, where they could undergo rapid molecular weight growth reactions to yield polycyclic aromatic nitrogen hydrocarbons (PANHs).

Predicting freeway pavement construction cost using a back-propagation neural network : a case study in Henan, China

The objective of this research was to develop a model to estimate future freeway pavement construction costs in Henan Province, China. A comprehensive set of factors contributing to the cost of freeway pavement construction were included in the model formulation. These factors comprehensively reflect the characteristics of region and topography and altitude variation, the cost of labour, material, and equipment, and time-related variables such as index numbers of labour prices, material prices and equipment prices. An Artificial Neural Network model using the Back-Propagation learning algorithm was developed to estimate the cost of freeway pavement construction. A total of 88 valid freeway cases were obtained from freeway construction projects let by the Henan Transportation Department during the period 1994−2007. Data from a random selection of 81 freeway cases were used to train the Neural Network model and the remaining data were used to test the performance of the Neural Network model. The tested model was used to predict freeway pavement construction costs in 2010 based on predictions of input values. In addition, this paper provides a suggested correction for the prediction of the value for the future freeway pavement construction costs. Since the change in future freeway pavement construction cost is affected by many factors, the predictions obtained by the proposed method, and therefore the model, will need to be tested once actual data are obtained.

Are in vitro estimates of cell diffusivity and cell proliferation rate sensitive to assay geometry?

Cells respond to various biochemical and physical cues during wound–healing and tumour progression. In vitro assays used to study these processes are typically conducted in one particular geometry and it is unclear how the assay geometry affects the capacity of cell populations to spread, or whether the relevant mechanisms, such as cell motility and cell proliferation, are somehow sensitive to the geometry of the assay. In this work we use a circular barrier assay to characterise the spreading of cell populations in two different geometries. Assay 1 describes a tumour–like geometry where a cell population spreads outwards into an open space. Assay 2 describes a wound–like geometry where a cell population spreads inwards to close a void. We use a combination of discrete and continuum mathematical models and automated image processing methods to obtain independent estimates of the effective cell diffusivity, D, and the effective cell proliferation rate, λ. Using our parameterised mathematical model we confirm that our estimates of D and λ accurately predict the time–evolution of the location of the leading edge and the cell density profiles for both assay 1 and assay 2. Our work suggests that the effective cell diffusivity is up to 50% lower for assay 2 compared to assay 1, whereas the effective cell proliferation rate is up to 30% lower for assay 2 compared to assay 1.

Analysis of strain-rate dependent mechanical behavior of single chondrocyte : a finite element study

Various studies have been conducted to investigate the effects of impact loading on cartilage damage and chondrocyte death. These have shown that the rate and magnitude of the applied strain significantly influence chondrocyte death, and that cell death occurred mostly in the superficial zone of cartilage suggesting the need to further understand the fundamental mechanisms underlying the chondrocytes death induced at certain levels of strain-rate. To date there is no comprehensive study providing insight on this phenomenon. The aim of this study is to examine the strain-rate dependent behavior of a single chondrocyte using a computational approach based on Finite Element Method (FEM). An FEM model was developed using various mechanical models, which were Standard Neo-Hookean Solid (SnHS), porohyperelastic (PHE) and poroviscohyperelastic (PVHE) to simulate Atomic Force Microscopy (AFM) experiments of chondrocyte. The PVHE showed, it can capture both relaxation and loading rate dependent behaviors of chondrocytes, accurately compared to other models.

A derivation of high-frequency asymptotic values of 3D added mass and damping based on properties of the Cummins' equation

This brief paper provides a novel derivation of the known asymptotic values of three-dimensional (3D) added mass and damping of marine structures in waves. The derivation is based on the properties of the convolution terms in the Cummins's Equation as derived by Ogilvie. The new derivation is simple and no approximations or series expansions are made. The results follow directly from the relative degree and low-frequency asymptotic properties of the rational representation of the convolution terms in the frequency domain. As an application, the extrapolation of damping values at high frequencies for the computation of retardation functions is also discussed.

Study on dynamic system optimum assignment to establish marginal time equilibrium

Several analytical methods for Dynamic System Optimum (DSO) assignment have been proposed but they are basically classified into two kinds. This chapter attempts to establish DSO by equilbrating the path dynamic marginal time (DMT). The authors analyze the path DMT for a single path with tandem bottlenecks and showed that the path DMT is not the simple summation of DMT associated with each bottleneck along the path. Next, the authors examined the DMT of several paths passing through a common bottleneck. It is shown that the externality at the bottleneck is shared by the paths in proportion to their demand from the current time until the queue vanishes. This share of the externality is caused by the departure rate shift under first in first out (FIFO) and the externality propagates to the downstream bottlenecks. However, the externalities propagates to the downstream are calculated out if downstream bottlenecks exist. Therefore, the authors concluded that the path DMT can be evaluated without considering the propagation of the externalities, but just as in the evaluation of the path DMT for a single path passing through a series of bottlenecks between the origin and destination. Based on the DMT analysis, the authors finally proposed a heuristic solution algorithm and verified it by comparing the numerical solution with the analytical one.

Exploration of mechanisms underlying the strain-rate-dependent mechanical property of single chondrocytes

Based on the characterization by Atomic Force Microscopy (AFM), we report that the mechanical property of single chondrocytes has dependency on the strain-rates. By comparing the mechanical deformation responses and the Young’s moduli of living and fixed chondrocytes at four different strain-rates, we explore the deformation mechanisms underlying this dependency property. We found that the strain-rate-dependent mechanical property of living cells is governed by both of the cellular cytoskeleton (CSK) and the intracellular fluid when the fixed chondrocytes is mainly governed by their intracellular fluid which is called the consolidation-dependent deformation behavior. Finally, we report that the porohyperelastic (PHE) constitutive material model which can capture the consolidation-dependent behavior of both living and fixed chondrocytes is a potential candidature to study living cell biomechanics.

Concerted HO2 elimination from alpha-Aminoalkylperoxyl free radicals : Experimental and theoretical evidence from the gas phase NH2 center dot CHCO2- + O-2 reaction

We have investigated the gas-phase reaction of the alpha-aminoacetate (glycyl) radical anion (NH2(sic)CHCO2-) with O-2 using ion trap mass spectrometry, quantum chemistry, and statistical reaction rate theory. This radical is found to undergo a remarkably rapid reaction with O-2 to form the hydroperoxyl radical (HO2(sic)) and an even-electron imine (NHCHCO2-), with experiments and master equation simulations revealing that reaction proceeds at the ion molecule collision rate. This reaction is facilitated by a low-energy concerted HO2(sic) elimination mechanism in the NH2CH(OO(sic))CO2- peroxyl radical. These findings can explain the widely observed free-radical-mediated oxidation of simple amino acids to amides plus alpha-keto acids (their imine hydrolysis products). This work also suggests that imines will be the main intermediates in the atmospheric oxidation of primary and secondary amines, including amine carbon capture solvents such as 2-aminoethanol (commonly known as monoethanolamine, or MEA), in a process that avoids the ozone-promoting conversion of (sic)NO to (sic)NO2 commonly encountered in peroxyl radical chemistry.

Using objective physical activity measures with youth : How many days of monitoring are needed?

Purpose The purpose of this study was to establish the minimal number of days of monitoring required for accelerometers to assess usual physical activity in children. Methods A total of 381 students (189 M, 192 F) wore a CSA 7164 uniaxial accelerometer for seven consecutive days. To examine age-related trends students were grouped as follows: Group I: grades 1-3 (N = 92); Group II: grades 4-6 (N = 98); Group III: grades 7-9 (N = 97); Group IV: grades 10-12 (N = 94). Average daily time spent in moderate-to-vigorous physical activity (MVPA) was calculated from minute-by-minute activity counts using the regression equation developed by Freedson et al. (1997). Results Compared with adolescents in grades 7 to 12, children in grades 1 to 6 exhibited less day-to-day variability in MVPA behavior. Spearman-Brown analysts indicated that between 4 and 5 d of monitoring would be necessary to a achieve a reliability of 0.80 in children, and between 8 and 9 d of monitoring would be necessary to achieve a reliability of 0.80 in adolescents. Within all grade levels, the 7-d monitoring protocol produced acceptable estimates of daily participation in MVPA (R = 0.76 (0.71-0.81) to 0.87 (0.84-0.90)). Compared with weekdays, children exhibited significantly higher levels of MVPA on weekends, whereas adolescents exhibited significantly lower levels of MVPA on weekends. Principal components analysis revealed two distinct time components for MVPA during the day for children (early morning, rest of the day), and three distinct time components for MVPA during the day for adolescents (morning, afternoon, early evening). Conclusions These results indicate that a 7-d monitoring protocol provides reliable estimates of usual physical activity behavior in children and adolescents and accounts for potentially important differences in weekend versus weekday activity behavior as well as differences in activity patterns within a given day.

Validity of the computer science and applications (CSA) activity monitor in children

Purpose The purpose of this study was to evaluate the validity of the CSA activity monitor as a measure of children's physical activity using energy expenditure (EE) as a criterion measure. Methods Thirty subjects aged 10 to 14 performed three 5-min treadmill bouts at 3, 4, and 6 mph, respectively. While on the treadmill, subjects wore CSA (WAM 7164) activity monitors on the right and left hips. (V) over dot O-2 was monitored continuously by an automated system. EE was determined by multiplying the average (V) over dot O-2 by the caloric equivalent of the mean respiratory exchange ratio. Results Repeated measures ANOVA indicated that both CSA monitors were sensitive to changes in treadmill speed. Mean activity counts from each CSA unit were not significantly different and the intraclass reliability coefficient for the two CSA units across all speeds was 0.87. Activity counts from both CSA units were strongly correlated with EE (r = 0.86 and 0.87, P < 0.001). An EE prediction equation was developed from 20 randomly selected subjects and cross-validated on the remaining 10. The equation predicted mean EE within 0.01 kcal.min(-1). The correlation between actual and predicted values was 0.93 (P < 0.01) and the SEE was 0.93 kcal.min(-1). Conclusion These data indicate that the CSA monitor is a valid and reliable tool for quantifying treadmill walking and running in children.

A comparison of mathematical models for phase separation in high-rate LiFePO4 cathodes

We construct a two-scale mathematical model for modern, high-rate LiFePO4cathodes. We attempt to validate against experimental data using two forms of the phase-field model developed recently to represent the concentration of Li+ in nano-sized LiFePO4crystals. We also compare this with the shrinking-core based model we developed previously. Validating against high-rate experimental data, in which electronic and electrolytic resistances have been reduced is an excellent test of the validity of the crystal-scale model used to represent the phase-change that may occur in LiFePO4material. We obtain poor fits with the shrinking-core based model, even with fitting based on “effective” parameter values. Surprisingly, using the more sophisticated phase-field models on the crystal-scale results in poorer fits, though a significant parameter regime could not be investigated due to numerical difficulties. Separate to the fits obtained, using phase-field based models embedded in a two-scale cathodic model results in “many-particle” effects consistent with those reported recently.

Predicting emotional exhaustion among haemodialysis nurses : a structural equation model using Kanter’s structural empowerment theory

Aim To test an explanatory model of the relationships between the nursing work environment, job satisfaction, job stress and emotional exhaustion for haemodialysis nurses, drawing on Kanter's theory of organizational empowerment. Background Understanding the organizational predictors of burnout (emotional exhaustion) in haemodialysis nurses is critical for staff retention and improving nurse and patient outcomes. Previous research has demonstrated high levels of emotional exhaustion among haemodialysis nurses, yet the relationships between nurses' work environment, job satisfaction, stress and emotional exhaustion in this population are poorly understood. Design A cross-sectional online survey. Methods 417 nurses working in haemodialysis units completed an online survey between October 2011–April 2012 using validated measures of the work environment, job satisfaction, job stress and emotional exhaustion. Results Overall, the structural equation model demonstrated adequate fit and we found partial support for the hypothesized relationships. Nurses' work environment had a direct positive effect on job satisfaction, explaining 88% of the variance. Greater job satisfaction, in turn, predicted lower job stress, explaining 82% of the variance. Job satisfaction also had an indirect effect on emotional exhaustion by mitigating job stress. However, job satisfaction did not have a direct effect on emotional exhaustion. Conclusion The work environment of haemodialysis nurses is pivotal to the development of job satisfaction. Nurses' job satisfaction also predicts their level of job stress and emotional exhaustion. Our findings suggest staff retention can be improved by creating empowering work environments that promote job satisfaction among haemodialysis nurses.

Statistical analysis of reduction in tensile strength of cotton strips as a measure of soil microbial activity

The cotton strip assay (CSA) is an established technique for measuring soil microbial activity. The technique involves burying cotton strips and measuring their tensile strength after a certain time. This gives a measure of the rotting rate, R, of the cotton strips. R is then a measure of soil microbial activity. This paper examines properties of the technique and indicates how the assay can be optimised. Humidity conditioning of the cotton strips before measuring their tensile strength reduced the within and between day variance and enabled the distribution of the tensile strength measurements to approximate normality. The test data came from a three-way factorial experiment (two soils, two temperatures, three moisture levels). The cotton strips were buried in the soil for intervals of time ranging up to 6 weeks. This enabled the rate of loss of cotton tensile strength with time to be studied under a range of conditions. An inverse cubic model accounted for greater than 90% of the total variation within each treatment combination. This offers support for summarising the decomposition process by a single parameter R. The approximate variance of the decomposition rate was estimated from a function incorporating the variance of tensile strength and the differential of the function for the rate of decomposition, R, with respect to tensile strength. This variance function has a minimum when the measured strength is approximately 2/3 that of the original strength. The estimates of R are almost unbiased and relatively robust against the cotton strips being left in the soil for more or less than the optimal time. We conclude that the rotting rate X should be measured using the inverse cubic equation, and that the cotton strips should be left in the soil until their strength has been reduced to about 2/3.

Assessing the role of spatial correlations during collective cell spreading

Spreading cell fronts are essential features of development, repair and disease processes. Many mathematical models used to describe the motion of cell fronts, such as Fisher’s equation, invoke a mean–field assumption which implies that there is no spatial structure, such as cell clustering, present. Here, we examine the presence of spatial structure using a combination of in vitro circular barrier assays, discrete random walk simulations and pair correlation functions. In particular, we analyse discrete simulation data using pair correlation functions to show that spatial structure can form in a spreading population of cells either through sufficiently strong cell–to–cell adhesion or sufficiently rapid cell proliferation. We analyse images from a circular barrier assay describing the spreading of a population of MM127 melanoma cells using the same pair correlation functions. Our results indicate that the spreading melanoma cell populations remain very close to spatially uniform, suggesting that the strength of cell–to–cell adhesion and the rate of cell proliferation are both sufficiently small so as not to induce any spatial patterning in the spreading populations.

Effect of hydrophilicity of carbon nanotube arrays on the release rate and activity of recombinant human bone morphogenetic protein-2

Novel nanostructures such as vertically aligned carbon nanotube (CNT) arrays have received increasing interest as drug delivery carriers. In the present study, two CNT arrays with extreme surface wettabilities are fabricated and their effects on the release of recombinant human bone morphogenetic protein-2 (rhBMP-2) are investigated. It is found that the superhydrophilic arrays retained a larger amount of rhBMP-2 than the superhydrophobic ones. Further use of a poloxamer diffusion layer delayed the initial burst and resulted in a greater total amount of rhBMP-2 released from both surfaces. In addition, rhBMP-2 bound to the superhydrophilic CNT arrays remained bioactive while they denatured on the superhydrophobic surfaces. These results are related to the combined effects of rhBMP-2 molecules interacting with poloxamer and the surface, which could be essential in the development of advanced carriers with tailored surface functionalities.