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Climate change is causing decreases in pH and dissolved oxygen (DO) in coastal ecosystems. Canopy-forming giant kelp can locally increase DO and pH through photosynthesis, with the most pronounced effect expected in surface waters where the bulk of kelp biomass resides. However, limited observations are available from waters in canopies and measurements at depth show limited potential of giant kelp to ameliorate chemical conditions. We quantified spatiotemporal variability of surface biogeochemistry and assessed the role of biological and physical drivers in pH and DO modification at two locations differing in hydrodynamics inside and outside of two kelp forests in Monterey Bay, California in summer 2019. pH, DO, dissolved inorganic carbon (DIC), and temperature were measured at and near the surface, in conjunction with physical parameters (currents and pressure), nutrients, and metrics of phytoplankton and kelp biological processes. DO and pH were highest, with lower DIC, at the surface inside kelp forests. However, differences inside vs. outside of kelp forests were small (DO 6–8%, pH 0.05 higher in kelp). The kelp forest with lower significant wave height and slower currents had greater modification of surface biogeochemistry as indicated by larger diel variation and slightly higher mean DO and pH, despite lower kelp growth rates. Differences between kelp forests and offshore areas were not driven by nutrients or phytoplankton. Although kelp had clear effects on biogeochemistry, which were modulated by hydrodynamics, the small magnitude and spatial extent of the effect limits the potential of kelp forests to mitigate acidification and hypoxia.more » « less
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Difluoroboron β-diketonate (BF 2 bdk) compounds show environment-sensitive optical properties in solution, aggregation-induced emission (AIE) and multi-stimuli responsive fluorescence switching in the solid state. Here, a series of 4-azepane-substituted β-diketone (bdk) ligands ( L-H , L-OMe , L-Br ) and their corresponding difluoroboron dyes ( D-H , D-OMe , D-Br ) were synthesized, and various responsive fluorescence properties of the compounds were studied, including solvatochromism, viscochromism, AIE, mechanochromic luminescence (ML) and halochromism. Compared to the β-diketones, the boron complexes exhibited higher extinction coefficients but lower quantum yields, and red-shifted absorption and emission in CH 2 Cl 2 . Computational studies showed that intramolecular charge transfer (ICT) dominated rather than π–π* transitions in all the compounds regardless of boron coordination. In solution, all the bdk ligands and boron dyes showed red-shifted emission in more polar solvents and increased fluorescence intensity in more viscous media. Upon aggregation, the emission of the β-diketones was quenched, however, the boronated dyes showed increased emission, indicative of AIE. Solid-state emission properties, ML and halochromism, were investigated on spin cast films. For ML, smearing caused a bathochromic emission shift for L-Br , and powder X-ray diffraction (XRD) patterns showed that the “as spun” and thermally annealed states were more crystalline and the smeared state was amorphous. No obvious ML emission shift was observed for L-H or L-OMe , and the boronated dyes were not mechano-active. Trifluoroacetic acid (TFA) and triethylamine (TEA) vapors were used to study halochromism. Large hypsochromic emission shifts were observed for all the compounds after exposure to TFA vapor, and reversible fluorescence switching was achieved using the acid/base pair.more » « less