A Silicon-Bridged Bis(substituted Cp) Yttrium Complex

rac-Bis(tetrahydrofuran)lithium [bis(2-trimethylsilyl-4-tert-butyl-η^5-cyclopentadienyl)dimethylsilane] dichloroyttrate, [Li(C_4H_80)_2][Y(C_(26)H_(48)-Si_3)Cl_2], M_r= 755.87, triclinic, Pl, ɑ = 13.110 (8), b = 17.163 (15), c = 20.623 (14) Å, ɑ= 104.02 (7), β = 99.38 (5), y = 100.24 (6)º, V = 4326 (6) Å^3, z = 4, D_x = 1.16 g cm^(-3), λ(Mo Kɑ)= 0.71073 Å, μ = 15.86 cm^(-1), F(000) = 1608, room temperature, R = 0.056 for 6136 reflections with F_o^2 > 3σ(F_o^2). There are two virtually identical molecules in the asymmetric unit. In each, the Y atom is tetrahedrally coordinated to a substituted Si-bridged bis(cyclopentadienyl) ligand and to two Cl ions in the cleft. The Li atom is 2.35 Å from each Cl ion, and two molecules of tetrahydrofuran are connected to the Li, completing its tetrahedral coordination

INTEGRATED REMOTE MONITORING FOR COASTAL GEOHAZARDS AND HERITAGE SITES

ABSTRACT In many regions of the world, coastal recession is a major issue. The coastal fringe represents a dynamic and complex setting, where numerous processes interact to shape the terrain. On certain coasts, these interactions can combine with local morphology to result in geohazards, such as slumps and mudflows. Such hazards can pose a major threat to human activities and areas rich in cultural heritage. There is a clear requirement for an effective monitoring strategy in order to assist those tasked with coastal management. However, traditional monitoring approaches tend to be spatially and temporally inadequate, and while significant research effort has concentrated on the application of more appropriate techniques, these are often unsuitable in isolation for monitoring of more complex morphology. This paper presents ongoing work on the development of an integrated, episodic monitoring strategy, primarily comprised of airborne and terrestrial laser scanning. In order to effectively integrate these datasets, software enabling weighted least squares surface matching has been developed. This gives the opportunity to register multi-source, multi-temporal datasets, allowing for change detection and analysis. Preliminary testing of this algorithm has been carried out on artificial datasets, and the results of these tests are presented and discussed. In addition, the development of a continuous GPS remote monitoring system is described, and the importance of historical datasets, and issues associated with this are discussed. The research is being applied to test sites on the North Yorkshire coast of eastern England, where geohazard features are commonplace

A Silicon-Bridged Bis(substituted Cp) Yttrium Complex

rac-Bis(tetrahydrofuran)lithium [bis(2-trimethylsilyl-4-tert-butyl-η^5-cyclopentadienyl)dimethylsilane] dichloroyttrate, [Li(C_4H_80)_2][Y(C_(26)H_(48)-Si_3)Cl_2], M_r= 755.87, triclinic, Pl, ɑ = 13.110 (8), b = 17.163 (15), c = 20.623 (14) Å, ɑ= 104.02 (7), β = 99.38 (5), y = 100.24 (6)º, V = 4326 (6) Å^3, z = 4, D_x = 1.16 g cm^(-3), λ(Mo Kɑ)= 0.71073 Å, μ = 15.86 cm^(-1), F(000) = 1608, room temperature, R = 0.056 for 6136 reflections with F_o^2 > 3σ(F_o^2). There are two virtually identical molecules in the asymmetric unit. In each, the Y atom is tetrahedrally coordinated to a substituted Si-bridged bis(cyclopentadienyl) ligand and to two Cl ions in the cleft. The Li atom is 2.35 Å from each Cl ion, and two molecules of tetrahydrofuran are connected to the Li, completing its tetrahedral coordination

Thermochemistry of Alane Complexes for Hydrogen Storage: A Theoretical and Experimental Comparison

Knowledge of the relative stabilities of alane (AlH3) complexes with electron donors is essential for identifying hydrogen storage materials for vehicular applications that can be regenerated by off-board methods; however, almost no thermodynamic data are available to make this assessment. To fill this gap, we employed the G4(MP2) method to determine heats of formation, entropies, and Gibbs free energies of formation for thirty-eight alane complexes with NH3-nRn (R = Me, Et; n = 0-3), pyridine, pyrazine, triethylenediamine (TEDA), quinuclidine, OH2-nRn (R = Me, Et; n = 0-2), dioxane, and tetrahydrofuran (THF). Monomer, bis, and selected dimer complex geometries were considered. Using these data, we computed the thermodynamics of the key formation and dehydrogenation reactions that would occur during hydrogen delivery and alane regeneration, from which trends in complex stability were identified. These predictions were tested by synthesizing six amine-alane complexes involving trimethylamine, triethylamine, dimethylethylamine, TEDA, quinuclidine, and hexamine, and obtaining upper limits of delta G for their formation from metallic aluminum. Combining these computational and experimental results, we establish a criterion for complex stability relevant to hydrogen storage that can be used to assess potential ligands prior to attempting synthesis of the alane complex. Based on this, we conclude that only a subset of the tertiary amine complexes considered and none of the ether complexes can be successfully formed by direct reaction with aluminum and regenerated in an alane-based hydrogen storage system.Comment: Accepted by the Journal of Physical Chemistry

Emplacement of inflated Pāhoehoe flows in the Naude’s Nek Pass, Lesotho remnant, Karoo continental flood basalt province: use of flow-lobe tumuli in understanding flood basalt emplacement

Physical volcanological features are presented for a 710-m-thick section, of the Naude’s Nek Pass, within the lower part of the Lesotho remnant of the Karoo Large Igneous Province. The section consists of inflated pāhoehoe lava with thin, impersistent sedimentary interbeds towards the base. There are seven discreet packages of compound and hummocky pāhoehoe lobes containing flow-lobe tumuli, making up approximately 50% of the section. Approximately 45% of the sequence consists of 14 sheet lobes, between 10 and 52-m-thick. The majority of the sheet lobes are in two packages indicating prolonged periods of lava supply capable of producing thick sheet lobes. The other sheet lobes are as individual lobes or pairs, within compound flows, suggesting brief increases in lava supply rate. We suggest, contrary to current belief, that there is no evidence that compound flows are proximal to source and sheet lobes (simple flows) are distal to source and we propose that the presence of flow-lobe tumuli in compound flows could be an indicator that a flow is distal to source. We use detailed, previously published, studies of the Thakurvadi Formation (Deccan Traps) as an example. We show that the length of a lobe and therefore the sections that are ‘medial or distal to source’ are specific to each individual lobe and are dependent on the lava supply of each eruptive event, and as such flow lobe tumuli can be used as an indicator of relative distance from source

An assessment of early colonisation of implant-abutment metal surfaces by single species and co-cultured bacterial periodontal pathogens

Objective Numerous studies have proposed that smooth metal surfaces reduce initial bacterial attachment in the establishment of an early biofilm formation. However, these studies have largely examined single bacterial species, which are not always relevant as pathogens identified as initiators of inflammatory peri-implantitis. This study investigated the adherence of four periodontally-relevant bacterial species to implant and abutment surfaces in current clinical use. Methods Discs of polished cobalt chromium (CoCr-polished) and milled titanium (Ti-milled), representing two clinically relevant surfaces, were prepared and surfaces were characterised. Bacterial species Porphyromonas gingivalis, Fusobacterium nucleatum, Prevotella intermedia and Aggregatibacter actinomycetemcomitans were cultured to mid-log or stationary growth phase. Co-cultures of P. gingivalis, F. nucleatum and P. gingivalis, F. nucleatum, Pr. intermedia were similarly prepared. Bacteria were inoculated onto discs for 2 h, stained with a live/dead fluorescent stain and percentage bacterial coverage was calculated by confocal microscopy and image analysis. Results CoCr-polished discs had smooth surfaces with gentle valley structures, whilst Ti-milled discs had sharp edged peaks. Both discs demonstrated a partial wetting ability capable of initiating bacterial adhesion. P. gingivalis, F. nucleatum and co-cultures, at both mid-log and stationary concentrations, demonstrated equally high coverage of both the smooth CoCr-polished and the rougher Ti-milled metal surfaces. Pr. intermedia and A. actinomycetemcomitans demonstrated lower surface coverage which was slightly higher for Ti-milled. Conclusion Variability was noted in the adherence potential for the respective periodontal pathogens examined. Particularly high adherence was noted for P. gingivalis and F. nucleatum, despite the manufacture of a smooth surface. Clinical significance Both surfaces studied may be used at implant-abutment junctions and both possess an ability to establish a bacterial biofilm containing a periodontally-relevant species. These surfaces are thus able to facilitate the apical migration of bacteria associated with peri-implantitis

Detectors for the James Webb Space Telescope Near-Infrared Spectrograph I: Readout Mode, Noise Model, and Calibration Considerations

We describe how the James Webb Space Telescope (JWST) Near-Infrared Spectrograph's (NIRSpec's) detectors will be read out, and present a model of how noise scales with the number of multiple non-destructive reads sampling-up-the-ramp. We believe that this noise model, which is validated using real and simulated test data, is applicable to most astronomical near-infrared instruments. We describe some non-ideal behaviors that have been observed in engineering grade NIRSpec detectors, and demonstrate that they are unlikely to affect NIRSpec sensitivity, operations, or calibration. These include a HAWAII-2RG reset anomaly and random telegraph noise (RTN). Using real test data, we show that the reset anomaly is: (1) very nearly noiseless and (2) can be easily calibrated out. Likewise, we show that large-amplitude RTN affects only a small and fixed population of pixels. It can therefore be tracked using standard pixel operability maps.Comment: 55 pages, 10 figure

Spectrum of KV2.1 Dysfunction in KCNB1‐Associated Neurodevelopmental Disorders

Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/152486/1/ana25607.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/152486/2/ana25607_am.pd

\u3cem\u3eLkb1\u3c/em\u3e Inactivation Drives Lung Cancer Lineage Switching Governed by Polycomb Repressive Complex 2

Adenosquamous lung tumours, which are extremely poor prognosis, may result from cellular plasticity. Here, we demonstrate lineage switching of KRAS+ lung adenocarcinomas (ADC) to squamous cell carcinoma (SCC) through deletion of Lkb1 (Stk11) in autochthonous and transplant models. Chromatin analysis reveals loss of H3K27me3 and gain of H3K27ac and H3K4me3 at squamous lineage genes, including Sox2, ΔNp63 and Ngfr. SCC lesions have higher levels of the H3K27 methyltransferase EZH2 than the ADC lesions, but there is a clear lack of the essential Polycomb Repressive Complex 2 (PRC2) subunit EED in the SCC lesions. The pattern of high EZH2, but low H3K27me3 mark, is also prevalent in human lung SCC and SCC regions within ADSCC tumours. Using FACS-isolated populations, we demonstrate that bronchioalveolar stem cells and club cells are the likely cells-of-origin for SCC transitioned tumours. These findings shed light on the epigenetics and cellular origins of lineage-specific lung tumours

The SOCS-Box of HIV-1 Vif Interacts with ElonginBC by Induced-Folding to Recruit Its Cul5-Containing Ubiquitin Ligase Complex

The HIV-1 viral infectivity factor (Vif) protein recruits an E3 ubiquitin ligase complex, comprising the cellular proteins elongin B and C (EloBC), cullin 5 (Cul5) and RING-box 2 (Rbx2), to the anti-viral proteins APOBEC3G (A3G) and APOBEC3F (A3F) and induces their polyubiquitination and proteasomal degradation. In this study, we used purified proteins and direct in vitro binding assays, isothermal titration calorimetry and NMR spectroscopy to describe the molecular mechanism for assembly of the Vif-EloBC ternary complex. We demonstrate that Vif binds to EloBC in two locations, and that both interactions induce structural changes in the SOCS box of Vif as well as EloBC. In particular, in addition to the previously established binding of Vif's BC box to EloC, we report a novel interaction between the conserved Pro-Pro-Leu-Pro motif of Vif and the C-terminal domain of EloB. Using cell-based assays, we further show that this interaction is necessary for the formation of a functional ligase complex, thus establishing a role of this motif. We conclude that HIV-1 Vif engages EloBC via an induced-folding mechanism that does not require additional co-factors, and speculate that these features distinguish Vif from other EloBC specificity factors such as cellular SOCS proteins, and may enhance the prospects of obtaining therapeutic inhibitors of Vif function