Annulation of Tetrathiafulvalene to the Bay Region of Perylenediimide: Fast Electron-Transfer Processes in Polar and Nonpolar Solvents

A tetrathiafulvalene donor has been annulated to the bay region of perylenediimide through a 1H-benzo-[d]pyrrolo[1,2-a]imidazol-1-one spacer affording an extended pi-conjugated molecular dyad (TTF-PDI). To gain insight into its ground- and excited-state electronic properties, the reference compound Ph-PDI has been prepared via a direct Schiff-base condensation of N,N'-bis(1-octylnonyl) benzoperylene-1',2':3,4:9,10-hexacarboxylic-1',2'-anhydride-3,4:9,10-bis (imide) with benzene-1,2-diamine. Both the experimental and the computational (DFT) results indicate that TTF-PDI exhibits significant intramolecular electronic interactions giving rise to an efficient photoinduced charge-separation process. Free-energy calculations verify that the process from TTF to the singlet-excited state of PDI is exothermic in both polar and nonpolar solvents. Fast adiabatic electron-transfer processes of a compactly fused, pi-conjugated TTF-PDI dyad in benzonitrile, 2-methyltetrahydrofuran, anisole and toluene were observed by femtosecond transient absorption spectral measurements. The lifetimes of radical-ion pairs slightly increase with decreasing the solvent polarities, suggesting that the charge-recombination occurs in the Marcus inverted region. By utilizing the nanosecond transient absorption technique, the intermolecular electron-transfer process in a mixture of has been observed via the triplet excited PDI for the first time.

Comparison of magnetic properties and petrography between dykes and lava flows from La Cienega, New Mexico and Thunder Bay area, Canada

Data on the evolution of geomagnetic paleointensity are crucial for understanding the geodynamo and Earth’s thermal history. Although basaltic flows are preferred for paleointensity experiments, quickly cooled mafic dykes have also been used. However, the paleointensity values obtained from the dykes are systematically lower than those from lava flows. This bias may originate from the difference in cooling histories and resultant magnetic mineralogies of extrusive and intrusive rocks. To explore this hypothesis, the magnetic mineralogy of two feeder dyke-lave flow systems, from Thunder Bay (Canada) and La Cienega (New-Mexico), has been studied using magnetic and microscopy methods. Within each system, the flow and dyke show different stages of deuteric oxidation of titanomagnetite, but the oxidation stages also differ between the two systems. It is concluded that the tested hypothesis is viable, but the relationships between the magnetic and mineralogical properties of flows and dykes are complex and need a further investigation.

Fish contaminants through the tribal perspective : an ethnography of the Keweenaw Bay Indian Community's tribal fish harvest

It has been well documented that many tribal populations and minority groups across the nation have been identified as being at high risk of the adverse health effects created by consuming fish that have been contaminated with mercury, PCBs, DDT, dioxins, and other chemicals. Although fish consumption advisories are intended to inform fish consumers of risks associated with specific species and water bodies, advisories have been the subject of both environmental injustices and treaty rights’ injustices. This means that understanding fish contaminants, through community perspectives is essential to good environmental policy. This study examined the fish contaminant knowledge, impacts on fishing and fish consumption, and the factors that contribute to harvesting decisions and behaviors in one tribal nation in the Upper Peninsula of Michigan, the Keweenaw Bay Indian Community. Using ethnographic methods, participant observation and semi-structured interviewing, fieldnotes were kept and all interviews were fully transcribed for data analysis. Among seventeen fishermen and women, contaminants are poorly understood, have had a limited impact on subsistence fishing but have had a substantial impact on commercial fishing activity. But ultimately, all decisions and behaviors are based on their own criteria and within a larger context of knowledge and understanding: the historical and cultural context. The historical context revealed that advisories are viewed as another attack on tribal fishing. The cultural context revealed that it is the fundamental guidance and essential framework associated with all harvesting beliefs, values, and traditional lifeways. These results have implications for advisories. ‘Fish’ and ‘contaminants’ appear differently based on the perceptions and priorities of those who encounter them.

A reinvestigation into the reaction of NH4OAc with acetyl derivatives of Bay-lis-Hillman adducts: Formation of tertiary and secondary allyl amines in-stead of primary allyl amines

A reinvestigation into the reaction between ammonium acetate and the acetyl derivatives of Baylis-Hillman adducts has led us to conclude that the products obtained are tertiary and secondary allyl amines and not the primary allyl amines. The unambiguous assignment of the structure of products using chemical and spectroscopic methods is described

Evaluation of the Role of Access Providers Discussion of Dutch Pirate Bay Case Law and Introducing Principles on Directness, Effectiveness, Costs, Relevance, and Time

Internet service providers (ISPs) play a pivotal role in contemporary society because they provide access to the Internet. The primary task of ISPs – to blindly transfer information across the network – has recently come under pressure, as has their status as neutral third parties. Both the public and the private sector have started to require ISPs to interfere with the content placed and transferred on the Internet as well as access to it for a variety of purposes, including the fight against cybercrime, digital piracy, child pornography, etc. This expanding list necessitates a critical assessment of the role of ISPs. This paper analyses the role of the access provider. Particular attention is paid to Dutch case law, in which access providers were forced to block The Pirate Bay. After analysing the position of ISPs, we will define principles that can guide the decisions of ISPs whether to take action after a request to block access based on directness, effectiveness, costs, relevance and time.

Benefits and challenges in practice-oriented psychotherapy research in Germany: The TK and the QS-PSY-BAY projects of quality assurance in outpatient psychotherapy

Objective: Two patient-focused long-term research projects performed in the German outpatient psychotherapy system are focused on in this article. The TK (Techniker Krankenkasse) project is the first study to evaluate a quality assurance and feedback system with regard to its practical feasibility in German routine care. The other study (“Quality Assurance in Outpatient Psychotherapy in Bavaria”; QS-PSY-BAY) was designed to test a new approach for quality assurance in outpatient psychotherapy using electronic documentation of patient characteristics and outcome parameters. In addition this project provides the opportunity to analyze data on health-related costs for the patients undergoing outpatient psychotherapy. Method: Both projects and their results indicating high effect sizes are briefly described. Results: From the perspectives of the research teams, advisory boards and other stakeholders, the experiences with these projects are discussed focusing on obstacles, challenges, difficulties, and benefits in developing and implementing the studies. The triangle collaboration of therapists, researchers, and health insurance companies/health service institutions turned out to be fruitful in both studies. Conclusions: Despite some controversies between the partners the experiences indicate the importance of practiced-research collaborations to provide relevant information about the delivery of outpatient psychotherapy in the health system

ʿAl has-sefînā ham-miṭṭārefet bay-yām!

dos Tzijonisṭiše Tzenṭral-Wahlkomiṭe

Keep at bay! - Abnormal personal space regulation as marker of paranoia in schizophrenia.

BACKGROUND During threat, interpersonal distance is deliberately increased. Personal space regulation is related to amygdala function and altered in schizophrenia, but it remains unknown whether it is particularly associated with paranoid threat. METHODS We compared performance in two tests on personal space between 64 patients with schizophrenia spectrum disorders and 24 matched controls. Patients were stratified in those with paranoid threat, neutral affect or paranoid experience of power. In the stop-distance paradigm, participants indicated the minimum tolerable interpersonal distance. In the fixed-distance paradigm, they indicated the level of comfort at fixed interpersonal distances. RESULTS Paranoid threat increased interpersonal distance two-fold in the stop-distance paradigm, and reduced comfort ratings in the fixed-distance paradigm. In contrast, patients experiencing paranoid power had high comfort ratings at any distance. Patients with neutral affect did not differ from controls in the stop-distance paradigm. Differences between groups remained when controlling for gender and positive symptom severity. Among schizophrenia patients, the stop-distance paradigm detected paranoid threat with 93% sensitivity and 83% specificity. CONCLUSIONS Personal space regulation is not generally altered in schizophrenia. However, state paranoid experience has distinct contributions to personal space regulation. Subjects experiencing current paranoid threat share increased safety-seeking behavior.