Glassy phases in organic semiconductors

Organic semiconductors may be processed from fluids using graphical arts printing and patterning techniques to create complex circuitry. Because organic semiconductors are weak van der Waals solids, the creation of glassy phases during processing is quite common. Because structural disorder leads to electronic disorder, it is necessary to understand these phases to optimize and control the electronic properties of these materials. Here we review the significance of glassy phases in organic semiconductors. We examine challenges in the measurement of the glass transition temperature and the accurate classification of phases in these relatively rigid materials. Device implications of glassy phases are discussed. Processing schemes that are grounded in the principles of glass physics and sound glass transition temperature measurement will more quickly achieve desired structure and electronic characteristics, accelerating the exciting progress of organic semiconductor technology development.     

The structural basis of molecular adaptation

Expression levels of fast-twitch (SERCA1), slow-twitch (SERCA2a) and "housekeeping" (SERCA2b) isoforms of the sarcoplasmic reticulum Ca(2+)-transport ATPase were monitored during regeneration of rat soleus muscles following necrosis induced by the toxin notexin at the tissue level by Western blot analysis and at the cellular level by immunocytochemical analysis. Due to necrosis, levels of muscle-specific SERCA1 and SERCA2a isoforms dropped to low levels on the third day after injection of the toxin. Subsequently, during regeneration both isoforms recovered but with a different time course. Expression of the fast type SERCA1 increased first. This type showed its most pronounced increase between day 3 and 10. Expression of the slow type SERCA2a was biphasic. After an increase to approximately one third of the control value on days 5-10, it showed its main increase up to the control level between day 10 and 21. Expression levels of the house-keeping SERCA2b isoform remained relatively constant throughout the 4 weeks of regeneration. Between day 10 and 28, when new innervation is established, SERCA2a expression spread gradually over almost all fibers whereas the number of SERCA1-expressing fibers decreased and only a limited number of fibers co-expressed SERCA1 and SERCA2a. At 4 weeks of regeneration, expression of the fast isoform was found only in 12% of the fibers, whereas the slow form was found in 98% of the fibers. In the contralateral untreated soleus muscles, 26% SERCA1-positive and 81% SERCA2a-positive fibers were observed. Immunocytochemical analysis showed that SERCA1 and SERCA2a were co-expressed with fast and slow myosin isoforms in fibers of normal muscles but in regenerated muscle only slow myosin and slow SERCA isoforms correlated. The results show that during regeneration levels of fast and slow SERCA proteins change in a similar way as their mRNAs do. However, in regenerated soleus, unlike in normal muscle, expression of slow SERCA is coregulated only with the slow myosin isoform. This finding is in agreement with the fact that the number of slow type fibers is increased in regenerated soleus.     

Matrix molecular orientation in fiber-reinforced polypropylene composites

A distinctive crystalline morphology which develops in certain fiber-reinforced thermoplastics, termed "transcrystallinity", occurs as the result of dense nucleation of polymer crystals at the surface of reinforcing fibers. As these fiber-sponsored nuclei grow, they impinge upon one another, such that crystal growth occurs essentially perpendicular to the fiber axis. Previous studies concerning transcrystallized composites have generally focused on single-fiber composites or model systems. Our interest is in elucidating the crystal orientation in conventional fiber-reinforced composites, and in quantifying the fraction of transcrystallized matrix, where present. In the present work, we develop a wide-angle X-ray scattering (WAXS) technique to investigate composites formed from an isotactic polypropylene (PP) matrix with practical loading levels of unidirectional pitch-based carbon, polyacrylonitrile (PAN)-based carbon, or aramid fibers. The transcrystalline fraction of the crystalline matrix approaches 0.95 in pitch-based carbon composites and 0.50 in the aramid composites near fiber loadings of 30 vol %. In addition, a previously-unreported mode of matrix orientation is observed in composites containing the non-transcrystallizing PAN-based carbon fibers, arising from restrictions on the isotropic growth of PP crystallites by the unidirectional fibers. This "constrained growth" orientation can coexist with the transcrystallized matrix at lower fiber loadings.     

Contribution of various substrates to total citric acid cycle flux and ]anaplerosis as determined by13C isotopomer analysis and O2 consumption in the heart

A simple relationship between parameters derived from a¹³C NMR isotopomer analysis and O₂ consumption is presented that allows measurement of the absolute rate of acetyl-CoA oxidation and anaplerotic flux in tissues oxidizing a mixture of four substrates. The method was first applied in a study of the effects of work state and -adrenergic stimulation on net acetate oxidation and anaplerosis in the isolated working rat heart. The results demonstrate that the anticipated ratio of 2 between O₂ consumption and TCA cycle flux for hearts oxidizing only acetate holds at low workload when anaplerosis is low, but deviates toward a factor of 3 under high workload conditions when anaplerosis is increased. This analysis was also extended to hearts that oxidize a more physiological mixture of substrates including long-chain fatty acids, acetoacetate, lactate, pyruvate, and glucose. We show that the contribution each substrate makes to total TCA cycle flux can be determined by combined¹³C NMR and O₂ consumption measurements. The present study also demonstrates that stimulation of anaplerosis (by addition of propionate) can significantly alter the relative contribution each substrate makes to total TCA cycle flux. We conclude that if¹³C labeling patterns are selected appropriately, a comprehensive picture of flux through all major metabolic pathways feeding the cycle can be determined in a single experiment even when complex physiological mixtures of substrates are provided.     

Credible sets for risk ratios in over-reported two-sample binomial data using the double-sampling scheme

We consider point and interval estimation for risk ratios based on two independent samples of binomial data subject to false positive misclassification. For such data it is well known that the model is unidentifiable. We consider incorporating training data obtained by using a double-sampling scheme to make the model identifiable. In this identifiable model, we propose a Bayesian method to make statistical inferences. In particular, we derive an easy-to-implement closed-form algorithm for drawing from the posterior distributions. The algorithm is illustrated using a real data example and further examined via Monte Carlo simulation studies.     

The effects of misspecified marginals and copulas on computing the value at risk: A Monte Carlo study

The effect on the estimation of the Value at Risk when dealing with multivariate portfolios when there is a misspecification both in the marginals and in the copulas is investigated. It is first shown that, when there is skewness in the data and symmetric marginals are used, the estimated elliptical (normal or t) copula correlations are negatively biased, reaching values as high as 70% of the true values. Besides, the bias almost doubles if negative correlations are considered, compared to positive correlations. As for the t copula degrees of freedom parameter, the use of wrong marginals delivers large positive biases, instead. If the dependence structure is represented by a copula which is not elliptical, e.g. the Clayton copula, the effects of marginal misspecifications on the copula parameter estimation can be rather different, depending on the sign of marginal skewness. Extensive Monte Carlo studies then show that the misspecifications in the marginal volatility equation more than offset the biases in copula parameters when VaR forecasting is of concern, small samples are considered and the data are leptokurtic. The biases in the volatility parameters are much smaller, whereas those ones in the copula parameters remain almost unchanged or even increase when the sample dimension increases. In this case, copula misspecifications do play a role for VaR estimation. However, these effects depend heavily on the sign of the dependence.     

Preliminary evaluation of electroencephalographic entrainment using thalamocortical modelling

Abstract: The concept of linked oscillators in biological control systems has long been established. Frequency entrainment is a predominant explanation behind many biological rhythms. In this paper a preliminary examination of electroencephalographic entrainment is made to survey the possibility and methods of achieving signal entrainment at the highest level of neurological organization and function. A model of the thalamocortical system is employed to generate simulated electroencephalographic signals and is tested in various configurations in the search for entrainment under very simple conditions. Additionally, an analysis of the coupled Van der Pol model of the circadian rhythm controller is performed to identify the possibility of affecting that system with a drastically different coupling input signal. We were able to conclude that overall signal shape can have a significant impact on the entrainment characteristics of the system. Due to the nature of the underlying mathematical structure of the model, by examining the circadian rhythm controller, we found that it is unsuitable for entrainment to an incident entraining signal of much higher frequency.