23 research outputs found

    Synthesis and characterization of titanium(IV) complexes containing the diphenylphosphino- and diphenylthiophosphoryl-functionalized cyclopentadienyl ligand. Crystal and molecular structure of Ti(η5-C5H4PPh2)Cl3

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    The trimethylsilyl cyclopentadiene derivative C5H4(SiMe3)PPh2 (1) was treated with TiCl4 to give the air- and moisture-sensitive mono(cyclopentadienyl) compound Ti(η5-C5H4PPh2)Cl3 (4). Reaction of 4 with Mg(CH2C6H5)2(THF)2 gave Ti(η5-C5H4PPh2)(CH2C6H5)3 (5). Reactions of the lithium and thallium derivatives M{C5H4P(S)Ph2} (M=Li (2), Tl (3)) with one equiv. of TiCl4 afforded the mono(cyclopentadienyl) complex Ti{η5-C5H4P(S)Ph2}Cl3 (6), whereas reaction with 0.5 equiv. of TiCl4 gave the bis(cyclopentadienyl) complex Ti{η5-C5H4P(S)Ph2}2Cl2 (8). Compound 6 was also isolated as a minor product from the reaction of Ti{η5-C5H4P(S)Ph2}2Cl2 (8) with one equiv. of TiCl4. The major product was identified as an inseparable mixture of two compounds [Ti{η5-C5H4P(S)Ph2}2Cl2·TiCl4]n (7a and 7b). Reaction of Ti(η5-C5H5)Cl3 with 3 afforded the ‘mixed-ring’ bis(cyclopentadienyl) complex Ti{η5-C5H4P(S)Ph2}(η5-C5H5)Cl2 (9). Compounds 6–9 are very moisture-sensitive and easily decompose to form the cyclopentadiene C5H5P(S)Ph2. Structural data of these complexes indicate η5-coordination of the substituted cyclopentadienyl ligands and this coordination mode was confirmed by X-ray crystal structure analysis of compound 4.We gratefully acknowledge financial support by DGICYT (ref. no. PB-97-0776), Iberdrola, and the Fonds der Chemischen Industrie

    REVIEW OF THE CENTRAL AND SOUTH ATLANTIC SHELF AND DEEP-SEA BENTHOS: SCIENCE, POLICY, AND MANAGEMENT

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    The Central and South Atlantic represents a vast ocean area and is home to a diverse range of ecosystems and species. Nevertheless, and similar to the rest of the global south, the area is comparatively understudied yet exposed to increasing levels of multisectoral pressures. To counteract this, the level of scientific exploration in the Central and South Atlantic has increased in recent years and will likely continue to do so within the context of the United Nations (UN) Decade of Ocean Science for Sustainable Development. Here, we compile the literature to investigate the distribution of previous scientific exploration of offshore (30 m+) ecosystems in the Central and South Atlantic, both within and beyond national jurisdiction, allowing us to synthesise overall patterns of biodiversity. Furthermore, through the lens of sustainable management, we have reviewed the existing anthropogenic activities and associated management measures relevant to the region. Through this exercise, we have identified key knowledge gaps and undersampled regions that represent priority areas for future research and commented on how these may be best incorporated into, or enhanced through, future management measures such as those in discussion at the UN Biodiversity Beyond National Jurisdiction negotiations. This review represents a comprehensive summary for scientists and managers alike looking to understand the key topographical, biological, and legislative features of the Central and South Atlantic.This paper is an output of the UN Ocean Decade endorsed Challenger 150 Programme (#57). Challenger 150 is supported by the Deep Ocean Stewardship Initiative (DOSI) and the Scientific Committee on Oceanic Research’s (SCOR) working group 159 (NSF Grant OCE-1840868) for which KLH is co-chair. AEHB, KLH, KAM, SBu, and KS are supported by the UKRI funded One Ocean Hub NE/S008950/1. TA is supported by the BiodivRestore ERA-NET Cofund (GA N°101003777) with the EU and the following funding organisations: FCT, RFCT, AEI, DFG, and ANR. TA also acknowledges financial support to CESAM by FCT/MCTES (UIDP/50017/2 020+UIDB/50017/2020+ LA/P/0094/2020) through national funds. NB is supported by the John Ellerman Foundation. AB is supported by the German Research Foundation. DH, CO, AFB, LA, SBr, and KS received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement no. 818123 (iAtlantic); this output reflects only the author’s view and the European Union cannot be held responsible for any use that may be made of the information contained therein. DH, AF, JT, and CW were additionally supported through the Cluster of Excellence “The Ocean Floor – Earth’s Uncharted Interface” (EXC-2077 – 390741603 by Deutsche Forschungsgemeinschaft). CO also extends thanks to the HWK – Institute for Advanced Study, and PM to Dr. Alberto Martín, retired professor of Universidad Simón Bolívar in Caracas, Venezuela for facilitating references used in the Venezuela section.Peer reviewe

    Validation of Multiplex Serology detecting human herpesviruses 1-5.

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    Human herpesviruses (HHV) cause a variety of clinically relevant conditions upon primary infection of typically young and immunocompetent hosts. Both primary infection and reactivation after latency can lead to more severe disease, such as encephalitis, congenital defects and cancer. Infections with HHV are also associated with cardiovascular and neurodegenerative disease. However, most of the associations are based on retrospective case-control analyses and well-powered prospective cohort studies are needed for assessing temporality and causality. To enable comprehensive investigations of HHV-related disease etiology in large prospective population-based cohort studies, we developed HHV Multiplex Serology. This methodology represents a low-cost, high-throughput technology that allows simultaneous measurement of specific antibodies against five HHV species: Herpes simplex viruses 1 and 2, Varicella zoster virus, Epstein-Barr virus, and Cytomegalovirus. The newly developed HHV species-specific ('Monoplex') assays were validated against established gold-standard reference assays. The specificity and sensitivity of the HHV species-specific Monoplex Serology assays ranged from 92.3% to 100.0% (median 97.4%) and 91.8% to 98.7% (median 96.6%), respectively. Concordance with reference assays was very high with kappa values ranging from 0.86 to 0.96 (median kappa 0.93). Multiplexing the Monoplex Serology assays resulted in no loss of performance and allows simultaneous detection of antibodies against the 5 HHV species in a high-throughput manner

    Physicochemical Properties of Three Ionic Liquids Containing a Tetracyanoborate Anion and Their Lithium Salt Mixtures

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    Given their relevant physicochemical properties, ionic liquids (ILs) are attracting great attention as electrolytes for use in different electrochemical devices, such as capacitors, sensors, and lithium ion batteries. In addition to the advantages of using ILs containing lithium cations as electrolytes in lithium ion batteries, the Li<sup>+</sup> transport in ILs containing the most common anion, bis­(trifluoromethanesulfonyl) imide anion ([Tf<sub>2</sub>N]), is reportedly small; therefore, its contribution to the overall conductivity is also low. In this work, we describe the preparation and characterization of two new and one known IL containing the tetracyanoborate anion ([B­(CN)<sub>4</sub>]) as the anionic species. These ILs have high thermal and chemical stabilities, with almost twice the ionic conductivity of the [Tf<sub>2</sub>N] ILs and, most importantly, provide a greater role for the Li<sup>+</sup> ion throughout the conductivity process. The experimental ionic conductivity and self-diffusion coefficient data show that the [B­(CN)<sub>4</sub>]-based ILs and their Li<sup>+</sup> mixtures have a higher number of charge carriers. Molecular dynamics simulations showed a weaker interaction between Li<sup>+</sup> and [B­(CN)<sub>4</sub>] than that with [Tf<sub>2</sub>N]. These results may stimulate new applications for ILs that have good Li<sup>+</sup> transport properties

    Increased Serological Response Against Human Herpesvirus 6A Is Associated With Risk for Multiple Sclerosis

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    Human herpesvirus (HHV)-6A or HHV-6B involvement in multiple sclerosis (MS) etiology has remained controversial mainly due to the lack of serological methods that can distinguish the two viruses. A novel multiplex serological assay measuring IgG reactivity against the immediate-early protein 1 from HHV-6A (IE1A) and HHV-6B (IE1B) was used in a MS cohort (8,742 persons with MS and 7,215 matched controls), and a pre-MS cohort (478 individuals and 476 matched controls) to investigate this further. The IgG response against IE1A was positively associated with MS (OR = 1.55, p = 9 × 10-22), and increased risk of future MS (OR = 2.22, p = 2 × 10-5). An interaction was observed between IE1A and Epstein-Barr virus (EBV) antibody responses for MS risk (attributable proportion = 0.24, p = 6 × 10-6). In contrast, the IgG response against IE1B was negatively associated with MS (OR = 0.74, p = 6 × 10-11). The association did not differ between MS subtypes or vary with severity of disease. The genetic control of HHV-6A/B antibody responses were located to the Human Leukocyte Antigen (HLA) region and the strongest association for IE1A was the DRB1*13:01-DQA1*01:03-DQB1*06:03 haplotype while the main association for IE1B was DRB1*13:02-DQA1*01:02-DQB1*06:04. In conclusion a role for HHV-6A in MS etiology is supported by an increased serological response against HHV-6A IE1 protein, an interaction with EBV, and an association to HLA genes
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