Reactivity of bridging thiocarbyne complexes of iron

The thiocarbyne cations, Cp(,2)Fe(,2)(CO)(,2)((mu)-CO)((mu)-CSR)(\u27+) (R = Me, Bz, All), react with a variety of nucleophiles (Nuc = H(\u27-), MeS(\u27-), PHS(\u27-), BzS(\u27-), PhSe(\u27-) and BzMgCl) to give bridging carbene complexes, Cp(,2)Fe(,2)(CO)(,2)((mu)-CO) (mu)-C(SR)Nuc . The cis-syn isomers of (mu)-hydridothiocarbene complexes, Cp(,2)Fe(,2)(CO)(,2)((mu)-CO) (mu)-C(H)SMe and Cp(,2)Fe(,2)(CO)(,2)((mu)-CO) (mu)-C(H)SCH(,2)Ph , have been isolated. In CDCl(,3), these complexes undergo a slow cis-syn to cis-anti interconversion and an even slower cis-syn/trans-syn isomerization. Solutions (in benzene, CHCl(,3), CH(,2)Cl(,2), acetone, and CH(,3)CN) of (mu)-dithiocarbene complexes, Cp(,2)Fe(,2)(CO)(,2)((mu)-CO) (mu)-C(SMe)SR , are equilibrium mixtures of all possible cis and trans isomers. The initially formed (mu)-selenothiocarbene complex, Cp(,2)Fe(,2)(CO)(,2)((mu)-CO) (mu)-C(SMe)SePh , converts to a (mu)-carbyne complex, Cp(,2)Fe(,2)(SePh)(CO)((mu)-CO)((mu)-CSMe), at 0(DEGREES)C. In contrast, the (mu)-dithiocarbene complex, Cp(,2)Fe(,2)(CO)(,2)((mu)-CO) (mu)-C(SMe)SPh , converts to Cp(,2)Fe(,2)(SPh)(CO)((mu)-CO)((mu)-CSMe) at 40(DEGREES)C;Reaction of Cp(,2)Fe(,2)(CO)(,2)((mu)-CO)((mu)-CSMe)(\u27+) with primary and secondary amines gives presumably the unstable complexes, CP(,2)Fe(,2)(SMe)(CO)((mu)-CO)((mu)-CNR(,2)). Tertiary amines do not react;A one electron reduction of Cp(,2)Fe(,2)(CO)(,2)((mu)-CO)((mu)-CSMe)(\u27+) gives the deep emerald green radical, Cp(,2)Fe(,2)(CO)(,2)((mu)-CO)((mu)-CSMe)(.), which has been characterized by IR, EPR and UV-visible spectroscopy. Ligand exchange reactions of Cp(,2)Fe(,2)(CO)(,2)((mu)-CO)((mu)-CSMe)(\u27+) are catalyzed by the radical, and apparently proceed through a mechanism involving dissociative loss of CO from Cp(,2)Fe(,2)(CO)(,2)((mu)-CO)((mu)-CSMe)(.);Reaction of Na Co(CO)(,4) with Cp(,2)Fe(,2)(CO)(,2)((mu)-CO)((mu)-CSMe)(\u27+) under UV photolysis gives Cp(,2)Fe(,2)Co(CO)(,3)((mu)-CO)(,2)((mu)(,3)-CSMe). An x-ray diffraction study of this cluster shows that it has an L-shaped triangular structure, but there is no Co-Fe bond on one edge of the triangle. The CSMe group bonds through the carbyne carbon to all three metals, and in addition the sulfur coordinates to the cobalt atom

Correcting second-order contamination in low-resolution spectra

An empirical method for correcting low-resolution astronomical spectra for second-order contamination is presented. The method was developed for correcting spectra obtained with grism #4 of the ALFOSC spectrograph at the Nordic Optical Telescope and the performance is demonstrated on spectra of two nearby bright Type Ia supernovae.Comment: accepted for publication in Astronomical Notes (Astronomische Nachrichten

Twitter for teaching: Can social media be used to enhance the process of learning?

Can social media be used to enhance the process of learning by students in higher education? Social media have become widely adopted by students in their personal lives. However, the application of social media to teaching and learning remains to be fully explored. In this study, the use of the social media tool Twitter for teaching was considered. Undergraduate students in Business and Management (n = 252) were encouraged to use Twitter for communicating with their tutor and each other during a 12-week course. Their involvement was evaluated using a survey considering amount of Twitter usage and students' attitudes and experiences. The data were analysed using factor analyses, which revealed a single usage construct and three attitudinal factors. Three findings emerged. Firstly, a positive correlation was found between amount of Twitter usage and student engagement in university-associated activities including organising their social lives and sharing information. Secondly, course-related tweeting was not related to interpersonal relationships between students and their tutor. Thirdly, Twitter usage did not impact class attendance. The results are salient for educational practitioners wishing to introduce social media into their teaching

Fundamental chemistry, Characterization, and Separation of Technetium Complexes in Hanford Waste

The ultimate goal of this proposal is to separate technetium from Hanford tank waste. Our recent work has shown that a large portion of the technetium is not pertechnetate (TcO4-) and is not easily oxidized. This has serious repercussions for technetium partitioning schemes because they are designed to separate this chemical form. Rational attempts to oxidize these species to TcO4- for processing or to separate the nonpertechnetate species themselves would be facilitated by knowing the identity of these complexes and understanding their fundamental chemistry. Tank characterization work has not yet identified any of the non-pertechnetate species. However, based on the types of ligands available and the redox conditions in the tank, a reasonable speculation can be made about the types of species that may be present. Thus, this proposal will synthesize and characterize the relevant model complexes of Tc(III), Tc(IV), and Tc(V) that may have formed under tank waste conditions. Once synthesized, these complexes will be used as standards for developing and characterizing the non-pertechnetate species in actual waste using instrumental techniques such as capillary electrophoresis electrospray mass spectrometry (CE-MS), x-ray absorbance spectroscopy (EXAFS and XANES), and multi-nuclear NMR (including 99Tc NMR). We will study the redox chemistry of the technetium complexes so that more efficient and selective oxidative methods can be used to bring these species to TcO4- for processing purposes. We will also study their ligand substitution chemistry, which could be used to develop separation methods for non-pertechnetate species. Understanding the fundamental chemistry of these technetium complexes will enable technetium to be efficiently removed from the Hanford tank waste and help DOE to fulfill its remediation mission

Internet-Delivered Dialectical Behavioral Therapy Skills Training for Chronic Pain: Protocol for a Randomized Controlled Trial

Background: Emotion dysregulation is key to the development and maintenance of chronic pain, feeding into a cycle of worsening pain and disability. Dialectical behavioral therapy (DBT), an evidence-based treatment for complex transdiagnostic conditions presenting with high emotion dysregulation, may be beneficial to manage and mitigate the emotional and sensory aspects of chronic pain. Increasingly, DBT skills training as a key component of standard DBT is being delivered as a stand-alone intervention without concurrent therapy to help develop skills for effective emotion regulation. A previous repeated-measure single-case trial investigating a novel technologically driven DBT skills training, internet-delivered DBT skills training for chronic pain (iDBT-Pain), revealed promising findings to improve both emotion dysregulation and pain intensity. Objective: This randomized controlled trial aims to examine the efficacy of iDBT-Pain in comparison with treatment as usual to reduce emotion dysregulation (primary outcome) for individuals with chronic pain after 9 weeks and at the 21-week follow-up. The secondary outcomes include pain intensity, pain interference, anxiety symptoms, depressive symptoms, perceived stress, posttraumatic stress, harm avoidance, social cognition, sleep quality, life satisfaction, and well-being. The trial also examines the acceptability of the iDBT-Pain intervention for future development and testing. Methods: A total of 48 people with chronic pain will be randomly assigned to 1 of 2 conditions: treatment and treatment as usual. Participants in the treatment condition will receive iDBT-Pain, consisting of 6 live web-based group sessions led by a DBT skills trainer and supervised by a registered psychologist and the iDBT-Pain app. Participants in the treatment-as-usual condition will not receive iDBT-Pain but will still access their usual medication and health interventions. We predict that iDBT-Pain will improve the primary outcome of emotion dysregulation and the secondary outcomes of pain intensity, pain interference, anxiety symptoms, depressive symptoms, perceived stress, harm avoidance, social cognition, sleep quality, life satisfaction, and well-being. A linear mixed model with random effects of individuals will be conducted to investigate the differences between the baseline, 9-week (primary end point), and 21-week (follow-up) assessments as a function of experimental condition. Results: Recruitment started in February 2023, and the clinical trial started in March 2023. Data collection for the final assessment is planned to be completed by July 2024. Conclusions: If our hypothesis is confirmed, our findings will contribute to the evidence for the efficacy and acceptability of a viable intervention that may be used by health care professionals for people with chronic pain. The results will add to the chronic pain literature to inform about the potential benefits of DBT skills training for chronic pain and will contribute evidence about technologically driven interventions

Legionella pneumophila strain 130b possesses a unique combination of type IV secretion systems and novel Dot/Icm secretion system effector proteins

Legionella pneumophila is a ubiquitous inhabitant of environmental water reservoirs. The bacteria infect a wide variety of protozoa and, after accidental inhalation, human alveolar macrophages, which can lead to severe pneumonia. The capability to thrive in phagocytic hosts is dependent on the Dot/Icm type IV secretion system (T4SS), which translocates multiple effector proteins into the host cell. In this study, we determined the draft genome sequence of L. pneumophila strain 130b (Wadsworth). We found that the 130b genome encodes a unique set of T4SSs, namely, the Dot/Icm T4SS, a Trb-1-like T4SS, and two Lvh T4SS gene clusters. Sequence analysis substantiated that a core set of 107 Dot/Icm T4SS effectors was conserved among the sequenced L. pneumophila strains Philadelphia-1, Lens, Paris, Corby, Alcoy, and 130b. We also identified new effector candidates and validated the translocation of 10 novel Dot/Icm T4SS effectors that are not present in L. pneumophila strain Philadelphia-1. We examined the prevalence of the new effector genes among 87 environmental and clinical L. pneumophila isolates. Five of the new effectors were identified in 34 to 62% of the isolates, while less than 15% of the strains tested positive for the other five genes. Collectively, our data show that the core set of conserved Dot/Icm T4SS effector proteins is supplemented by a variable repertoire of accessory effectors that may partly account for differences in the virulences and prevalences of particular L. pneumophila strains. Copyright © 2010, American Society for Microbiology. All Rights Reserved

Enhanced Control of PWR Primary Coolant Water Chemistry Using Selective Separation Systems for Recovery and Recycle of Enriched Boric Acid

The objective of this project is to develop systems that will allow for increased nuclear energy production through the use of enriched fuels. The developed systems will allow for the efficient and selective recover of selected isotopes that are additives to power water reactors' primary coolant chemistry for suppression of corrosion attack on reactor materials

An H-alpha survey aiming at the detection of extraplanar diffuse ionized gas in halos of edge-on spiral galaxies II. The H-alpha survey atlas and catalog

In this second paper on the investigation of extraplanar diffuse ionized gas in nearby edge-on spiral galaxies we present the actual results of the individual galaxies of our H-alpha imaging survey. A grand total of 74 galaxies have been studied, including the 9 galaxies of a recently studied sub-sample (Rossa & Dettmar 2000). 40.5% of all studied galaxies reveal extraplanar diffuse ionized gas, whereas in 59.5% of the survey galaxies no extraplanar diffuse ionized gas could be detected. The average distances of this extended emission above the galactic midplane range from 1-2 kpc, while individual filaments in a few galaxies reach distances of up to |z| ~ 6 kpc. In several cases a pervasive layer of ionized gas was detected, similar to the Reynolds layer in our Milky Way, while other galaxies reveal only extended emission locally. The morphology of the diffuse ionized gas is discussed for each galaxy and is compared with observations of other important ISM constituents in the context of the disk-halo connection, in those cases where published results were available. Furthermore, we present the distribution of extraplanar dust in these galaxies, based on an analysis of the unsharp-masked R-band images. The results are compared with the distribution of the diffuse ionized gas.Comment: LaTeX, 21 pages, 7 figures, accepted for publication in A&A, figs. 22-54 are only available in electronic form and figs. 2-11 + 17-20 are also available at http://www.astro.rub.de/jrossa/ha-surve

Photo-elicitation: using photographs to read retail interiors through consumers' eyes

Researchers studying experiences in retail environments have typically restricted their attention towards examining the influence of individual atmospheric variables upon customer behavior. In this respect photographs and video are common environmental simulation techniques. This research approach not only concerns researchers active in consumer culture theory, but also interior architects and retail designers. As holistic inspired practitioners, they maintain that interiors function as 'Gestalt' environments, interacting with their users. Inspired by their viewpoints, in this paper, the authors reflect on the use of the inductive, holistically inspired method of photo-elicitation in research concerning experiences in retail environments. In addition, they report on the application of photo-elicitation in two empirical projects. The findings demonstrate the value of photo-elicitation in gaining insight into customer experiences in retail interiors