239 research outputs found
An analytical survey and study of counseling attitudes and practices of Baptist clergymen in New England
Thesis (Ed.M.)--Boston Universit
Cp*Fe(Me2PCH2CH2PMe2)(CHO) : hydride shuttle reactivity of a thermally stable formyl complex.
[Cp*Fe(Me2PCH2CH2PMe2)(CO)]+ [BArF24]− has been synthesised and characterised using single crystal X-ray diffraction, NMR and IR spectroscopies. Reduction of the CO ligand using Na[Et3BH] produces the corresponding neutral formyl complex Cp*Fe(Me2PCH2CH2PMe2)(CHO), that is very thermally stable, and which is attributed to the electron-releasing properties of the spectator ligands. This compound is a potent hydride donor which exists in equilibrium with [Et3BH]−, Et3B, and the structural isomer (η4-C5Me5H)Cp*Fe(Me2PCH2CH2PMe2)(CO), resulting from reversible hydride migration to the Cp* ligand
Teaching old compounds new tricks: efficient N2 fixation by simple Fe(N2)(diphosphine)2 complexes
The Fe(0) species Fe(N2)(dmpe)2 exists in equilibrium with the previously unreported dimer, [Fe(dmpe2)2(μ-N2)]. For the first time these complexes, alongside Fe(N2)(depe)2, are shown unambiguously to produce N2H4 and/or NH3 upon addition of triflic acid; for Fe(N2)(depe)2 this represents one of the highest electron conversion efficiencies for Fe complexes to date
MicroED Characterization of a Robust Cationic -Alkane Complex Stabilized by the [B(3,5-(SF5)2C6H3)4]– Anion, via On-Grid Solid/Gas Single-Crystal to Single-Crystal Reactivity
Microcrystalline (~1 m) [Rh(Cy2PCH2CH2PCy2)(norbornadiene)][S-BArF4], [S-BArF4] = [B(3,5-(SF5)2C6H3)4]–, reacts with H2 in a single-crystal to single-crystal transformation to form the -alkane complex [Rh(Cy2PCH2CH2PCy2)(norbornane)][S-BArF4], for which the structure was determined by microcrystal Electron Diffraction (microED), to 0.95 Å resolution, via an on-grid hydrogenation, and a complementary single-crystal X-ray diffraction study on larger, but challenging to isolate, crystals. Comparison with the [BArF4]– analogue [ArF = 3,5-(CF3)2C5H3)] shows that the [S-BArF4]– anion makes the -alkane complex robust towards decomposition both thermally and when suspended in pentane. Subsequent reactivity with dissolved ethene in a pentane slurry, forms [Rh(Cy2PCH2CH2PCy2)(ethene)2][S-BArF4], and the catalytic dimerisation/isomerisation of ethene to 2-butenes. The increased stability of [S-BArF4]– salts is identified as being due to increased non-covalent interactions in the lattice, resulting in a solid-state molecular organometallic material with desirable stability characteristics
Selectivity of Rh⋅⋅⋅H−C Binding in a σ-Alkane Complex Controlled by the Secondary Microenvironment in the Solid State
By using single-crystal to single-crystal solid-state molecular organometallic (SMOM) techniques, the σ -alkane complex [Rh( t Bu 2 PCH 2 CH 2 CH 2 P t Bu 2 )( η 2 , η 2 -C 7 H 12 )][BAr F 4 ] (Ar F = 3,5-(CF 3 ) 2 C 6 H 3 ) is synthesized and structurally characterized, in which the alkane (norbornane) binds through two exo -C-H···Rh interactions. In contrast, the bis-cyclohexyl phosphine analogue shows endo -alkane binding. Comparison of the two systems, supported by periodic DFT calculations, NCI plots and Hirshfeld surface analyses, trace this different regioselectivity to subtle changes in the local microenvironment surrounding the alkane ligand. A tertiary periodic structure supporting a secondary microenvironment that controls binding at the metal site has parallels with enzymes. The new σ -alkane complex is also a catalyst for solid/gas 1-butene isomerization, and catalyst resting states are identified for this
Derivation of High Spatial Resolution Albedo from UAV Digital Imagery:Application over the Greenland Ice Sheet
Measurements of albedo are a prerequisite for modeling surface melt across the Earth's cryosphere, yet available satellite products are limited in spatial and/or temporal resolution. Here, we present a practical methodology to obtain centimeter resolution albedo products with accuracies of ?5% using consumer-grade digital camera and unmanned aerial vehicle (UAV) technologies. Our method comprises a workflow for processing, correcting and calibrating raw digital images using a white reference target, and upward and downward shortwave radiation measurements from broadband silicon pyranometers. We demonstrate the method with a set of UAV sorties over the western, K-sector of the Greenland Ice Sheet. The resulting albedo product, UAV10A1, covers 280 km2, at a resolution of 20 cm per pixel and has a root-mean-square difference of 3.7% compared to MOD10A1 and 4.9% compared to ground-based broadband pyranometer measurements. By continuously measuring downward solar irradiance, the technique overcomes previous limitations due to variable illumination conditions during and between surveys over glaciated terrain. The current miniaturization of multispectral sensors and incorporation of upward facing radiation sensors on UAV packages means that this technique could become increasingly common in field studies and used for a wide range of applications. These include the mapping of debris, dust, cryoconite and bioalbedo, and directly constraining surface energy balance models.publishersversionPeer reviewe
'Countries in the Air': Travel and Geomodernism in Louis MacNeice's BBC Features
In the middle stretch of his twenty-two-year BBC career, the poet and producer Louis MacNeice earned a reputation as one of the ‘undisputed masters of creative sound broadcasting’, a reputation derived, in part, from a huge range of radio features that were founded upon his journeys abroad. Through close examination of some of his most significant overseas soundscapes – including Portrait of Rome (1947) and Portrait of Delhi (1948) – this article will consider the role and function of travel in shaping MacNeice’s engagement with the radio feature as a modernist form at a particular transcultural moment when Britain moved through the end of the Second World War and the eventual disintegration of its empire
A Mixed Blessing: Market-Mediated Religious Authority in Neopaganism
This research explores how marketplace dynamics affect religious authority in the context of Neopagan religion. Drawing on an interpretivist study of Wiccan practitioners in Italy, we reveal that engagement with the market may cause considerable, ongoing tensions, based on the inherent contradictions that are perceived to exist between spirituality and commercial gain. As a result, market success is a mixed blessing that can increase religious authority and influence, but is just as likely to decrease authority and credibility. Using an extended case study method, we propose a theoretical framework that depicts the links between our informants’ situated experiences and the macro-level factors affecting religious authority as it interacts with market-mediated dynamics at the global level. Overall, our study extends previous work in macromarketing that has looked at religious authority in the marketplace) and how the processes of globalization are affecting religion
Targeted Morphoproteomic Profiling of Ewing's Sarcoma Treated with Insulin-Like Growth Factor 1 Receptor (IGF1R) Inhibitors: Response/Resistance Signatures
Insulin-like growth factor 1 receptor (IGF1R) targeted therapies have resulted in responses in a small number of patients with advanced metastatic Ewing's sarcoma. We performed morphoproteomic profiling to better understand response/resistance mechanisms of Ewing's sarcoma to IGF1R inhibitor-based therapy.This pilot study assessed two patients with advanced Ewing's sarcoma treated with IGF1R antibody alone followed by combined IGF1R inhibitor plus mammalian target of rapamycin (mTOR) inhibitor treatment once resistance to single-agent IGF1R inhibitor developed. Immunohistochemical probes were applied to detect p-mTOR (Ser2448), p-Akt (Ser473), p-ERK1/2 (Thr202/Tyr204), nestin, and p-STAT3 (Tyr 705) in the original and recurrent tumor. The initial remarkable radiographic responses to IGF1R-antibody therapy was followed by resistance and then response to combined IGF1R plus mTOR inhibitor therapy in both patients, and then resistance to the combination regimen in one patient. In patient 1, upregulation of p-Akt and p-mTOR in the tumor that relapsed after initial response to IGF1R antibody might explain the resistance that developed, and the subsequent response to combined IGF1R plus mTOR inhibitor therapy. In patient 2, upregulation of mTOR was seen in the primary tumor, perhaps explaining the initial response to the IGF1R and mTOR inhibitor combination, while the resistant tumor that emerged showed activation of the ERK pathway as well.Morphoproteomic analysis revealed that the mTOR pathway was activated in these two patients with advanced Ewing's sarcoma who showed response to combined IGF1R and mTOR inhibition, and the ERK pathway in the patient in whom resistance to this combination emerged. Our pilot results suggests that morphoproteomic assessment of signaling pathway activation in Ewing's sarcoma merits further investigation as a guide to understanding response and resistance signatures
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