Tuning the Dimensions of C60‐Based Needlelike Crystals in Blended Thin Films

A new ordered structure of the C₆₀ derivative PCBM ([6‐6]‐phenyl C₆₁‐butyric acid methyl ester) is obtained in thin films based on the blend PCBM:regioregular P3HT (poly(3‐hexylthiophene)). Rapid formation of needlelike crystalline PCBM structures of a few micrometers up to 100 μm in size is demonstrated by submitting the blended thin films to an appropriate thermal treatment. These structures can grow out to a 2D network of PCBM needles and, in specific cases, to spectacular PCBM fans. Key parameters to tune the dimensions and spatial distribution of the PCBM needles are blend ratio and annealing conditions. The as‐obtained blended films and crystals are probed using atomic force microscopy, transmission electron microscopy, selected area electron diffraction, optical microscopy, and confocal fluorescence microscopy. Based on the analytical results, the growth mechanism of the PCBM structures within the film is described in terms of diffusion of PCBM towards the PCBM crystals, leaving highly crystalline P3HT behind in the surrounding matrix.     

Mortality in a cohort of men expressing the glucose-6-phosphate dehydrogenase deficiency

The objective of this study was to test the hypothesis of a lower mortality from cancer and cardiovascular diseases among men expressing glucose-6-phosphate dehydrogenase (G6PD) deficiency. We designed a mortality study based on death certificates from January 1, 1982 through December 31, 1992 in a cohort of G6PD-deficient men. Cohort members were 1,756 men, identified as expressing the G6PD-deficient phenotype during a 1981 population screening of the G6PD polymorphism. The setting was the island of Sardinia, Italy. Outcome measures were cause-specific standardized mortality ratios (SMRs), which were computed as 100 times the observed/expected ratio, with the general Sardinian male population as the reference. Deaths from all causes were significantly less than expected due to decreased SMRs for ischemic heart disease (SMR, 28; 95% confidence interval [CI], 10 to 62), cerebrovascular disease (SMR, 22; 95% CI, 6 to 55), and liver cirrhosis (SMR, 12; 95% CI, 0 to 66), which explained 95.6% of the deficit in total mortality. All cancer mortality was close to the expectation, with a significant increase in the SMR for non-Hodgkin's lymphoma (SMR, 545; 95% CI, 147 to 1,395). A decrease in mortality from cardiovascular diseases was one of the study hypotheses, based on an earlier human report and experimental evidence. However, selection bias is also a likely explanation. Further analytic studies are warranted to confirm whether subjects expressing the G6PD-deficient phenotype are protected against ischemic heart disease and cerebrovascular disease. This cohort study is consistent with more recent case-control studies in rejecting the hypothesis of a decreased cancer risk among G6PD-deficient subjects. The observed increase in mortality from non-Hodgkin's lymphoma and decrease in mortality from liver cirrhosis were not previously reported.     

Discrete Time Non-Homogeneous Semi-Markov Reliability Transition Credit Risk Models and the Default Distribution Functions

This paper shows how to apply discrete time non-homogeneous semi-Markov processes (DTNHSMP) with an age index to credit risk. The idea is to consider the credit risk problem as a reliability model indexed by the age and in this way, many semi-Markov results could be adapted to describe credit risk problem. The default state is seen as a “non working state”. As the semi-Markov process is a generalization of Markov process, the presented model can be seen as a more general migration model. In fact, in semi-Markov environment the distribution function (d.f.) of the waiting time before a transition can be of any type and without the strong constraints of the Markov model. Furthermore, some results on the asymptotic behavior of the presented model are given. This permits the construction of the d.f. of the default random variable for each “working state”. An example, constructed manipulating some Standard & Poor’s (S&P) data, is presented.     

Estimation of spatial-temporal gait parameters in level walking based on a single accelerometer: Validation on normal subjects by standard gait analysis

This paper investigates the ability of a single wireless inertial sensing device stuck on the lower trunk to provide spatial-temporal parameters during level walking. The 3-axial acceleration signals were filtered and the timing of the main gait events identified. Twenty-two healthy subjects were analyzed with this system for validation, and the estimated parameters were compared with those obtained with state-of-the-art gait analysis, i.e. stereophotogrammetry and dynamometry. For each side, from four to six gait cycles were measured with the device, of which two were validated by gait analysis. The new acquisition system is easy to use and does not interfere with regular walking. No statistically significant differences were found between the acceleration-based measurements and the corresponding ones from gait analysis for most of the spatial-temporal parameters, i.e. stride length, stride duration, cadence and speed, etc.; significant differences were found for the gait cycle phases, i.e. single and double support duration, etc. The system therefore shows promise also for a future routine clinical use.     

Ester-functionalized poly(3-alkylthiophene) copolymers: Synthesis,physicochemical characterization and performance in bulk heterojunction organic solar cells

The introduction of functional moieties in the donor polymer (side chains) offers a potential pathway toward selective modification of the nanomorphology of conjugated polymer:fullerene active layer blends applied in bulk heterojunction organic photovoltaics, pursuing morphology control and solar cell stability. For this purpose, two types of poly(3-alkylthiophene) random copolymers, incorporating different amounts (10/30/50%) of ester-functionalized side chains, were efficiently synthesized using the Rieke method. The solar cell performance of the functionalized copolymers was evaluated and compared to the pristine P3HT:PCBM system. It was observed that the physicochemical and opto-electronic characteristics of the polythiophene donor material can be modified to a certain extent via copolymerization without (too much) jeopardizing the OPV efficiency, as far as the functionalized side chains are introduced in a moderate ratio (<30%) and that preference is given to side chains with a small molar volume. A range of complementary techniques – UV–Vis spectroscopy, (modulated temperature) differential scanning calorimetry, transmission electron microscopy and X-ray diffraction analysis – indicated that variations in polymer crystallinity, while maintaining a high level of regioregularity, are probably the main factor responsible for the observed differences.     

Coding procedures to analyse interaction patterns in educational web forums

Analysis of interaction patterns is one of the most important indicators of quality of learning in educational web forums. Social network analysis (SNA) is gradually assuming importance in the study of interaction patterns as it focuses on the analysis of the interrelationships between individuals, thus providing a holistic perspective on group performance. However, most of the studies that use SNA in computer-supported collaborative learning scenarios derive their data from server log files, on the assumption that this data source reflects the way people really interacted online. This study, the purpose of which is to better understand the communication flows that really occur among users, challenges these assumptions through an experimental study that makes a comparison between the structural method normally used to detect the posting addressees and an approach enriched with semantic coding. Results show that this new coding schema, if compared with traditional structural coding, detected a greater number of addressees, thus allowing a greater number of postings to be included in an SNA adjacency matrix.     

Valuing credit default swap in a non-homogeneous semi-Markovian rating based model

In this paper, we use a discrete time non-homogeneous semi-Markov model for the rating evolution of the credit quality of a firm C (see D’Amico, Janssen, and Manca Proceedings of the II international workshop in applied probablity, 2004a) and we determine the credit default swap spread for a contract between two parties, A and B that, respectively, sell and buy a protection about the failure of the firm C. We work both in the case of deterministic and stochastic recovery rate. We also highlight the link between credit risk and reliability theory.