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At least 1,603 records · Page 89

Nanoconfinement-induced shift in photooxidative degradation pathway of polystyrene

Polymer nanocomposites with high concentrations of nanoparticles (NPs) possess exceptional mechanical, transport, and thermal properties. To enable their widespread use in structural applications and functional coatings, it is crucial to understand how nanoconfinement and the polymer-NP interface influence polymer degradation under various environmental conditions, including prolonged UV exposure. In this study, we investigate the photooxidative degradation of polystyrene (PS)-confined in the interstices of SiO 2 NP films. These nanocomposite films are prepared by the capillary rise infiltration (CaRI) of PS into interstices of SiO 2 NP packings, and subsequently subjected to UV irradiation. Our investigation reveals that PS degradation progresses uniformly across the thickness, with degradation initiating from the center of the NP interstitial pores and extending towards the NP surface. We rationalize this degradation mechanism based on the disparity in the surface energies of PS and the NP surface, as well as slow oxygen diffusion through confined PS. Here, we also demonstrate that packing smaller NPs at a given thickness or thicker packing of a specific NP size facilitates photooxidative degradation, highlighting the critical role of the number of interstitial pores in influencing degradation processes.

36 MATERIALS SCIENCE↗

ENSO regimes and the late 1970's climate shift: The role of synoptic weather and South Pacific ocean spiciness

South Pacific subtropical density compensated temperature and salinity (spiciness) anomalies are known to be associated with decadal equatorial variability, however, the mechanisms by which such disturbances are generated, advect and the degree to which they modulate the equatorial thermocline remains controversial. During the late 1970's a climate regime transition preceded a period of strong and sustained El Nino events. Using an ocean general circulation model forced by the constituent mechanical and thermodynamic components of the reanalysed atmosphere we show that the late 1970's transition coincided with the arrival of a large-scale, subsurface cold and fresh water anomaly in the central tropical Pacific. An ocean reanalysis for the period 1990–2007 that assimilates subsurface Argo, XBT and CTD data, reveals that disturbances occur due to the subduction of negative surface salinity anomalies from near 30° S, 100° W which are advected along the σ=25–26 kgm{sup −3} isopycnal surfaces. These anomalies take, on average, seven years to reach the central equatorial Pacific where they may substantially perturb the thermocline before the remnants ultimately ventilate in the region of the western Pacific warm pool. Positive (warm–salty) disturbances, known to occur due to late winter diapycnal mixing and isopycnal outcropping, arise due to both subduction of subtropical mode waters and subsurface injection. On reaching the equatorial band (10° S–0° S) these disturbances tend to deepen the thermocline reducing the model's ENSO. In contrast the emergence of negative (cold–fresh) disturbances at the equator are associated with a shoaling of the thermocline and El Nino events. Process studies are used to show that the generation and advection of anomalous density compensated thermocline disturbances critically depend on stochastic forcing of the intrinsic ocean by weather. We further show that in the absence of the inter-annual component of the atmosphere forcing Central Pacific El Nino events are manifest.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Shifting groundwater fluxes in bedrock fractures: Evidence from stream water radon and water isotopes

Geologic features (e.g., fractures and alluvial fans) can play an important role in the locations and volumes of groundwater discharge and degree of groundwater-surface water (GW-SW) interactions. However, the role of these features in controlling GW-SW dynamics and streamflow generation processes are not well constrained. GW-SW interactions and streamflow generation processes are further complicated by variability in precipitation inputs from summer and fall monsoon rains, as well as declines in snowpack and changing melt dynamics driven by warming temperatures. Using high spatial and temporal resolution radon and water stable isotope sampling and a 1D groundwater flux model, we evaluated how groundwater contributions and GW-SW interactions varied along a stream reach impacted by fractures (fractured-zone) and below the fractured hillslope (non-fractured zone) in Coal Creek, a Colorado River headwater stream affected by summer monsoons. During early summer, groundwater contributions from the fractured zone dominated, but declined throughout the summer. Groundwater contributions from the non-fractured zone were constant throughout the summer and became proportionally more important later in the summer. We hypothesize that groundwater in the non-fractured zone is dominantly sourced from a high-storage alluvial fan at the base of a tributary that is connected to Coal Creek throughout the summer and provides consistent groundwater influx. Water isotope data revealed that Coal Creek responds quickly to incoming precipitation early in the summer, and summer precipitation becomes more important for streamflow generation later in the summer. We quantified the change in catchment dynamic storage and found it negatively related to stream water isotope values, and positively related to modeled groundwater discharge and the ratio of fractured zone to non-fractured zone groundwater. Importantly, we interpret these relationships as declining hydrologic connectivity throughout the summer leading to late summer streamflow supported predominantly by shallow flow paths, with variable response to drying from geologic features based on their storage. As groundwater becomes more important for sustaining summer flows, quantifying local geologic controls on groundwater inputs and their response to variable moisture conditions may become critical for accurate predictions of streamflow.

54 ENVIRONMENTAL SCIENCES↗

12-hour Shifts for Radiation Therapists

In Canada, Radiation Therapy program hours have ranged between 8 and 10 hours a day. Some centres have an option of a 4-day, 10-hour-day workweek. In 2012, Cancer Care Ontario released their Radiation Treatment Capital Investment Strategy. In this, they mandated that in order to maximize the use of current infrastructure, cancer centres will need to be operational for 12 hours in the future. This strategy was supported by a cost-benefit analysis.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Phosphine and N-heterocyclic carbene ligands on Pt(II) shift selectivity from ethylene hydrophenylation toward benzene vinylation

In this study, a series of Pt(II) complexes of the type ([(L~L)Pt(L')(Ph)][BAr' 4 ] (L~L = 1,2-bis(dimethylphosphino)ethane, 1,2-bis(diphenylphosphino)ethane, ( N -pyrrolyl) 2 P(CH 2 ) 2 P( N -pyrrolyl) 2 , 1,3-bis(diphenylphosphino)propane, 1,1'-bis(diphenylphosphino)ferrocene, (bis-(diphenylphosphino)methyl)methylamine, 8-(diisopropylphosphino)quinoline, 1,1'-methylene-3,3'-di- tert -butylimidazol-2,2'-diylidine); L' = THF or NCMe) has been synthesized and fully characterized. These complexes were screened as catalysts for ethylene hydrophenylation to yield ethylbenzene. All of the complexes exhibited selectivity for styrene production with low catalytic turnover. DFT calculations have been used to model reactivity of the [(dmpe)Pt(L')(Ph)][BAr' 4 ] (dmpe = 1,2-bis(dimethylphosphino)ethane). It is shown that selective styrene formation is a result of a calculated ΔΔ G ‡ of 5 kcal/mol for the benzene C–H activation step in the catalytic cycles for styrene versus ethylbenzene formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Shifting temporal dynamics of human mobility in the United States

In this paper we analyze the average hourly temporal dynamics of human mobility in the United States from 2019 to 2020. We discuss how large decreases in human mobility nonuniformly effect the daily temporal dynamics of aggregate human behavior. The data used are weekly activity patterns for POIs from 2019 to 2020 in the United States, provided by SafeGraph and made openly available to academic and research institutions. We use clustering methods to create metrics describing how human activity changes throughout the day/week at the county and national levels. In response to significant mobility reductions starting March 2020, daily temporal patterns of human activity changed nonuniformly. Morning activity started later, and evening activity started earlier in 2020 compared to 2019, and temporal behavioral patterns on weekdays began to look more similar to weekends. The changes in daily temporal behavior persisted throughout the year even as total mobility levels recovered. The results provide insights on the changes in human behavior in response covid-19 policies and illustrate influences on social systems, health, and transportation networks.

99 GENERAL AND MISCELLANEOUS↗