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Due to their strong luminescent properties, transition metal polypyridine complexes have garnered a great deal of attention, and are finding numerous applications in materials science, biomedicine, and catalysis. Strong spin-orbit coupling in these complexes leads to long triplet excited state lifetimes which are central to the development of materials and methods important to biomedicine such as optical blood gas sensors. The recent discovery of bis- and tris-cyclometalated platinum(IV) complexes has opened up new potential in this area as some of these complexes exhibit extreme sensitivity to molecular oxygen and lifetimes hundreds of microseconds long. Therefore, the synthesis of materials with very long lifetimes and a high sensitivity to triplet oxygen has been undertaken. New platinum(IV) complexes are being investigated using judicious modification of metal-ligand architectures to yield very long lifetimes. Efforts are focusing upon modifying the nature of the excited state to promote greater charge transfer through я system extension and constraint of ring rotation. Ligands are being synthesized using a combination of the Krohnke pyridine synthesis and Suzuki cross-coupling reactions. To synthesize bis- and tris-cylcometalated platinum(IV) complexes, cyclometalated platinum(II) pendant complexes will be oxidized using hypervalent iodine reagents followed by ligand substitution.

Photoactive materials have gained widespread interest amongst researchers given their ability to harness and redirect the energy of photons. Photon absorption by the material can enable normally unfeasible chemical reactions, promote electron transfer/flow, or be re-emitted. This versatility makes these compounds indispensible to areas of research such as light-emitting devices, dye-sensitized solar cells, photocatalytic hydrogen production, and optical oxygen sensors. The focus of this dissertation is the development of novel compounds for such purposes. Synthetic methodologies were developed to produce two new families of phosphorescent platinum compounds. Chapter 2 discusses a family of 16 cyclometalated platinum(II) diimine complexes derived from four cyclometalating ligands and four diimine ligands. The versatility of the synthetic process is demonstrated and the complexes are fully characterized via NMR spectroscopy, mass spectrometry, and elemental analysis. The complexes demonstrate green phosphorescence from a ligand centered state (∼500 nm), while the minimal contribution from the metal-to-ligand charge transfer state did not go unnoticed. The photophysical and electrochemical qualities of the complexes are described, and their excited state dynamics explained. Chapter 3 accounts the synthesis and characterization of a novel family of 11 bis-cyclometalated platinum(IV) complexes. The synthetic route included utilizing cyclometalated platinum(II) pendant complexes for a second, oxidation-facilitated cyclometalation to arrive at the precursor bis-cyclometalated platinum(IV) dichlorides. These complexes were converted to the heteroleptic diimine complexes via ligand substitution. All complexes exhibited long-lived triplet excited states (1-260μs), and some showed particularly efficient oxygen quenching. Excited state dynamics as predicted by static DFT calculations were proven inaccurate by experimental data, and time-dependent DFT was utilized to account for this discrepancy. The newly developed synthetic procedures have provided numerous opportunities for continued research. Specifically, the synthesis of mixed-ligand bis-cyclometalated platinum(IV) complexes, and platinum(IV) species with other ancillary ligands such as acetylacetonate, cyanide, and N-heterocyclic carbenes, are routes to new luminescent materials which will be explored.

Science archives are cornerstones of modern astronomical facilities. In this paper we describe the version 1.0 milestone of the Atacama Large Millimeter/submillimeter Array Science Archive. This version features a comprehensive query interface with rich metadata and visualisation of the spatial and spectral locations of the observations, a complete set of virtual observatory services for programmatic access, text-based similarity search, display and query for types of astronomical objects in SIMBAD and NED, browser-based remote visualisation, interactive previews with tentative line identification and extensive documentation including video and Jupyter Notebook tutorials. The development is regularly evaluated by means of user surveys and is entirely focused on providing the best possible user experience with the goal of helping to maximise the scientific productivity of the observatory.

The Atacama Large Millimeter/submillimeter Array (ALMA), an international partnership of Europe, North America and East Asia in cooperation with the Republic of Chile, is the largest astronomical project in existence. While ALMA's capabilities are ramping up, Early Science observations have started. The ALMA Archive is at the center of the operations of the telescope array and is designed to manage the 200 TB of data that will be taken each year, once the observatory is in full operations. We briefly describe design principles. The second part of this paper focuses on how astronomy is likely to evolve as the amount and complexity of data taken grows. We argue that in the future observatories will compete for astronomers to work with their data, that observatories will have to reorient themselves to from providing good data only to providing an excellent end-to-end user-experience with all its implications, that science-grade data-reduction pipelines will become an integral part of the design of a new observatory or instrument and that all this evolution will have a deep impact on how astronomers will do science. We show how ALMA's design principles are in line with this paradigm.

Good Counsel's girls' swim team won its sixth consecutive National Catholic High School Championship yesterday. Senior All-Met Rachael Burke won her fourth 500 yard freestyle title with a Villanova University pool record time of 4 minutes 53.31 seconds. Burke had won the previous three 500-yard freestyle races at the meet. Paul VI Catholic finished third. Burke also won the 200 freestyle and anchored the 200 medley and 400 freestyle relay teams. Her younger sister, Amanda, finished second in both the 200 and 500. Georgetown Prep's season is a huge improvement from its last two campaigns -- the Little Hoyas finished 4-14-1 the past two years. [Brian Boland] credits the turnaround to a solid defense and new goaltender, sophomore A.J. Minite.

During direct communication between two cells, the plasma membranes of each cell serve as a platform for ligand‐receptor interaction initiating downstream signaling cascades. In immune cell signaling, this cell–cell interface – the immune synapse – is highly spatiotemporally organized. Multiple stimulatory and co‐stimulatory signals need to be integrated over time to ensure proper immune cell function. This process is still not fully understood given the vast complexity of interactions between proteins, lipids, glycocalyx and associated cortical actin cytoskeleton. Here, we presented a fully artificial model system to study the interface between two vesicles and a semi‐artificial one between a live cell and a vesicle to reconstitute 3D contacts. We investigated the distribution and reorganization of immune cell proteins at artificial and semi‐artificial contacts. We show the enrichment and depletion of different proteins in the synapse and how different peptides with varying affinity presented by the same MHC class I affect T cell activation. We further explored the distribution of glycocalyx elements and showed differential partitioning of different sugar moieties in the interface. While we focused on the T cell interface here, our model systems are powerful tools to study the distribution and reorganization of lipids, proteins and glycocalyx components at any cell–cell contact. A comprehensive understanding of the interactions between proteins, lipids and glycocalyx components at the immune synapse is still lacking. Here, an artificial and a semi‐artificial model contact system were established to reconstitute the cell‐cell contact in 3D. The model systems enable the examination of macromolecule enrichment or depletion at the contact in the context of T cell signalling and beyond.

PurposeAs more patients undergo lumbar spine surgery, novel interventions may improve physical and mental health outcomes. Few studies summarize the benefit of cognitive behavioral therapy (CBT) among lumbar spine surgery patients. This study collects randomized control trial data to investigate the influence of CBT on patient reported outcomes among lumbar spine surgery patients.MethodsOur study used the Preferred Reporting Items for Systematic Reviews and Meta-Analyses and a medical library expert assisted in searching PubMed/MEDLINE, Scopus, CINAHL, Cochrane Central Register of Controlled Trials, Cochrane Database of Systematic Reviews, PsycINFO, and Google Scholar. We calculated standardized mean differences (SMD) to evaluate the effect size of CBT versus control groups with a sensitivity analysis.ResultsOur meta-analysis included seven studies with a total of 531 patients. The majority of included studies evaluated lumbar fusion, with preoperative CBT performed by physiotherapists. The largest effects were observed for overall quality of life (SMD = 0.55 [95% CI 0.05, 1.05], p < 0.001, I2 = 86.7%) and psychological outcomes (SMD = 0.61 [95% CI 0.28, 0.94], p < 0.001, I2 = 89.7%) though disability and pain outcomes also favored CBT intervention. Included studies demonstrated low overall bias but large heterogeneity. Sensitivity analysis demonstrated negligible study design differences and revealed moderators including CBT session frequency and final follow-up duration (p < 0.001).ConclusionCompared to usual care or alternative therapy control arms, CBT delivered the most improvement with overall quality of life and psychological outcomes. Among appropriately selected patients, CBT could improve perioperative disability, pain, quality of life, and psychological health following lumbar spine surgery.

The sensitivity of the αβ T cell receptor (TCR) is enhanced by the coreceptors CD4 and CD8αβ, which are expressed primarily by cells of the helper and cytotoxic T cell lineages, respectively. The coreceptors bind to major histocompatibility complex (MHC) molecules and associate intracellularly with the Src-family kinase Lck, which catalyzes TCR phosphorylation during receptor triggering. Although coreceptor/kinase occupancy was initially believed to be high, a recent study suggested that most coreceptors exist in an Lck-free state, and that this low occupancy helps to effect TCR antigen discrimination. Here, using the same method, we found instead that the CD4/Lck interaction was stoichiometric (~100%) and that the CD8αβ/Lck interaction was substantial (~60%). We confirmed our findings in live cells using fluorescence cross-correlation spectroscopy (FCCS) to measure coreceptor/Lck codiffusion in situ. After introducing structurally guided mutations into the intracellular domain of CD4, we used FCCS to also show that stoichiometric coupling to Lck required an amphipathic α-helix present in CD4 but not CD8α. In double-positive cells expressing equal numbers of both coreceptors, but limiting amounts of kinase, CD4 outcompeted CD8αβ for Lck. In T cells, TCR signaling induced CD4/Lck oligomerization but did not affect the high levels of CD4/ Lck occupancy. These findings help settle the question of kinase occupancy and suggest that the binding advantages that CD4 has over CD8 could be important when Lck levels are limiting.

INTRODUCTION:Among patients with chronic laryngeal symptoms, ambulatory reflux monitoring off acid suppression is recommended to evaluate for laryngopharyngeal reflux (LPR). However, reflux monitoring systems are diverse in configuration and monitoring capabilities, which present a challenge in creating a diagnostic reference standard in these patients. This study aimed to compare diagnostic yield and performance between reflux monitoring systems in patients with chronic laryngeal symptoms.METHODS:This multicenter, international study of adult patients referred for evaluation of LPR over a 5-year period (March 2018-May 2023) assessed and compared diagnostic yield of pathologic gastroesophageal reflux (GER+) on ambulatory reflux monitoring off acid suppression.RESULTS:Of 813 patients, 296 (36%) underwent prolonged wireless pH, 532 (65%) underwent 24-hour pH-impedance monitoring, and 15 (2%) underwent both tests. Overall diagnostic yield for GER+ was 36% and greater for prolonged wireless pH compared with that for 24-hour pH-impedance monitoring (50% vs 27%; P < 0.01). Among 15 patients who underwent both prolonged wireless pH and 24-h pH-impedance monitoring, concordance between systems for GER+ was 40%. The most common source of discordance was strong evidence of GER+ across multiple days on prolonged wireless pH compared with no evidence of GER+ on pH-impedance.DISCUSSION:In this multicenter international study of patients with chronic laryngeal symptoms referred for LPR evaluation, diagnostic yield of ambulatory reflux monitoring off acid suppression was 36% and rose to 50% when using wireless pH monitoring. In patients referred for chronic laryngeal symptoms, 24-hour pH-impedance monitoring may risk a low negative predictive value in patients with unproven GER+ disease.

Diverse food system resilience frameworks and assessment tools are being developed to measure food system performance in the face of disruptive events. The divide between academic research and gray literature can result in inaccessibility of assessment tools to communities and non-academic researchers. The authors performed a literature review and selected seven urban food system resilience assessment frameworks for comparison with resilience attributes, as well as consideration of their intended audience; spatial scope; data type; data collection; strengths; and ease of use. The frameworks were found to match between three and seven of the ten identified resilience attributes, with a range of intended audiences. Framework data collection methodologies included surveys, spatial data analysis, and mixed methods approaches to collect quantitative, semi-quantitative, and qualitative data. Most of the included frameworks include flexible indicators and metrics for investigators to collect relevant data for their planning goals. While the ability to develop unique metrics can be a strength, undefined metrics present an issue for non-academic researchers in communities seeking to effectively assess their own food system. Limitations in existing assessment tools include a wide range of intended outcomes and burdensome data collection. The comparison of the assessment tools resulted in recommendations of frameworks for academic and non-academic researchers and revealed gaps including a lack of fair labor considerations. This review allows researchers to develop effective frameworks for diverse users to prioritize resilience in food systems.