Studies of an Fe9 tridiminished icosahedron

The synthesis and structural characterization of a nonanuclear FeIII cage complex is reported. The nine iron centers in [Fe9(mu3-O)4(O3PPh)3(O2CCMe3)13] lie on the vertices of an incomplete icosahedron, with the P atoms of triphenylphosphonate at the other three vertices. The paramagnetic core therefore describes a tridiminished icosahedron. Magnetic studies suggest an S=1/2 ground state for the molecule. Analysis of exchange paths and the susceptibility data point to the interpretation that the cluster can be divided into two nearly decoupled sections: an {Fe6O3} section, with an S=0 ground state, in which three oxo-centered triangles bound a central triangle that is not oxo-centered; and an {Fe3O} triangle with S=1/2. The analysis of the susceptibility data leads to a Heisenberg model based on three significant antiferromagnetic exchange interactions, with values of 173.7 cm-1 in the {Fe3O} triangle, and 30.9 and 19.1 cm-1 within the {Fe6O3} section, while the exchange between them is <1 cm-1. With these assignments, the theoretical low-temperature differential susceptibility is also in very good agreement with measurements up to 50 T. Magnetic measurements in the milli-kelvin range reveal striking hysteresis loops and magnetization reversals associated with a Landau-Zener-Stückelberg (LZS) transition as enhanced by the occurrence of a phonon bottleneck.     

Quantum mechanical investigation of the atmospheric reaction CH3O2 + NO

The important stationary points on the potential energy surface of the reaction CH(3)O(2) + NO have been investigated using ab initio and density functional theory techniques. The optimizations were carried out at the B3LYP/6-311++G(d,p) and MP2/6-311++G(d,p) levels of theory while the energetics have been refined using the G2MP2, G3//B3LYP, and CCSD(T) methodologies. The calculations allow the proper characterization of the transition state barriers that determine the fate of the nascent association conformeric minima of methyl peroxynitrite. The main products, CH(3)O + NO(2), are formed through either rearrangement of the trans-conformer to methyl nitrate and its subsequent dissociation or via the breaking of the peroxy bond of the cis-conformer to CH(3)O + NO(2) radical pair. The important consequences of the proposed mechanism are (a) the allowance on energetic grounds for nitrate formation parallel to radical propagation under favorable external conditions and (b) the confirmation of the conformational preference of the homolytic cleavage of the peroxy bond, discussed in previous literature.     

Credit risk assessment: a challenge for financial institutions

^** E-mail: vangeli3{at}eaee.gr This study explores financial credit risk assessment. This isan important issue because there is currently no standardizedmethod used by financial institutions for the assessment ofcredit risk. A critical evaluation of the most popular creditrisk assessment methods—the judgmental method, credit-scoringand portfolio models—highlights a number of limitationswhen used on their own. Several interviewees confirm that creditrisk assessment methods should be combined for effective creditrisk assessment. Accordingly, the study proposes a frameworkfor improving credit risk assessment, which combines the strengthsof these methods and copes successfully with their limitations.     

Active stereo sound localization

Estimating the direction of arrival of sound in three-dimensional space is typically performed by generalized time-delay processing on a set of signals from a fixed array of omnidirectional microphones. This requires specialized multichannel A/D hardware, and careful arrangement of the microphones into an array. This work is motivated by the desire to instead only use standard two-channel audio A/D hardware and portable equipment. To estimate direction of arrival of persistent sound, the position of the microphones is made variable by mounting them on one or more computer-controlled pan-and-tilt units. In this paper, we describe the signal processing and control algorithm of a device with two omnidirectional microphones on a fixed baseline and two rotational degrees of freedom. Experimental results with real data are reported with both impulsive and speech sounds in an untreated, normally reverberant indoor environment.     

Inference of a minimum size boolean function from examples by using a new efficient branch-and-bound approach

This paper deals with the problem of identifying a hidden Boolean function : 0, 1' 0, 1 from positive and negative examples. This problem is of paramount importance in many real life applications of artificial intelligence. The method proposed in this paper is based on a branch-and-bound approach. This approach is an expansion of some earlier work (Triantaphyllouet al., 1994). Computational results, comparing the new method with one based on Karmakar's interior point method, suggest that the new method is very efficient.     

In Silico Investigation of the Biological Implications of Complex DNA Damage with Emphasis in Cancer Radiotherapy through a Systems Biology Approach

Different types of DNA lesions forming in close vicinity, create clusters of damaged sites termed as “clustered/complex DNA damage” and they are considered to be a major challenge for DNA repair mechanisms resulting in significant repair delays and induction of genomic instability. Upon detection of DNA damage, the corresponding DNA damage response and repair (DDR/R) mechanisms are activated. The inability of cells to process clustered DNA lesions efficiently has a great impact on the normal function and survival of cells. If complex lesions are left unrepaired or misrepaired, they can lead to mutations and if persistent, they may lead to apoptotic cell death. In this in silico study, and through rigorous data mining, we have identified human genes that are activated upon complex DNA damage induction like in the case of ionizing radiation (IR) and beyond the standard DNA repair pathways, and are also involved in cancer pathways, by employing stringent bioinformatics and systems biology methodologies. Given that IR can cause repair resistant lesions within a short DNA segment (a few nm), thereby augmenting the hazardous and toxic effects of radiation, we also investigated the possible implication of the most biologically important of those genes in comorbid non-neoplastic diseases through network integration, as well as their potential for predicting survival in cancer patients.     

Monitoring of Polycyclic Aromatic Hydrocarbon Levels in Mussels (Mytilus galloprovincialis) from Aquaculture Farms in Central Macedonia Region,Greece, Using Gas Chromatography–Tandem Mass Spectrometry Method

A new sensitive and selective gas chromatography tandem mass spectrometry (GC-MS/MS) method was developed for the analysis of 26 polycyclic aromatic hydrocarbons (PAHs), including 16 Environmental Protection Agency (EPA) and 15 + 1 European Union (EU) PAHs, in mussel samples from aquaculture farms in Thermaikos and Strymonian Gulf, Central Macedonia Region, in three sampling periods. Concentrations were found at moderate to low values at all sampling sites, without exceeding maximum levels set by EU. Low molecular weight PAHs were predominant in all samples. Seasonal variation of the concentrations was observed; values were slightly higher in the winter period. Use of diagnostic ratios for potential sources of PAHs showed both petrogenic and pyrolitic origin. In comparison to other related studies of mussels from the Mediterranean Sea, Greek mussels cultivated in the studied gulfs are low in contaminants due to minimal environmental pollution effects. Low concentrations of PAHs are in compliance with the low values of other POPs which were found in the mussels.     

Studying Physiological Synchrony in Couple Therapy through Partial Directed Coherence: Associations with the Therapeutic Alliance and Meaning Construction

In line with the growing recognition of the role of embodiment, affect and implicit processes in psychotherapy, several recent studies examine the role of physiological synchrony in the process and outcome of psychotherapy. This study aims to introduce Partial Directed Coherence (PDC) as a novel approach to calculating psychophysiological synchrony and examine its potential to contribute to our understanding of the therapy process. The study adopts a single-case, mixed-method design and examines physiological synchrony in one-couple therapy in relation to the therapeutic alliance and a narrative analysis of meaning construction in the sessions. Interpersonal Physiological Synchrony (IPS) was calculated, via a windowed approach, through PDC of a Heart Rate Variability-derived physiological index, which was measured in the third and penultimate sessions. Our mixed-method analysis shows that PDC quantified significant moments of IPS within and across the sessions, modeling the characteristics of interpersonal interaction as well as the effects of therapy on the interactional dynamics. The findings of this study point to the complex interplay between explicit and implicit levels of interaction and the potential contribution of including physiological synchrony in the study of interactional processes in psychotherapy.