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Cesiated complexes of the aliphatic amino acids (Gly, Ala, hAla, Val, Leu, and Ile) were examined by infrared multiple photon dissociation (IRMPD) action spectroscopy utilizing light from a free-electron laser (FEL). To identify structures, the experimental spectra were compared to linear spectra calculated at the B3LYP-GD3BJ/def2-TZVP level of theory. Relative energies at 0 and 298 K for various possible conformers of all complexes were calculated at B3LYP, B3LYP-GD3BJ, and MP2(full) levels using the def2-TZVP basis set. Spectral comparison for all complexes indicates that the dominant conformation has the cesium cation binding to the carbonyl and hydroxyl oxygens, [CO,OH]. This conclusion contrasts with previous work for Cs+(Gly), which suggested that the [CO] binding motif was prevalent. This dichotomy is explored theoretically in detail using coupled-cluster calculations with single, double, and perturbative triple excitations, CCSD(T), as well as advanced density functional theory (DFT) approaches. The comparisons show that the [CO,OH] – [CO] double-well potential found for most DFT approaches disappears at the higher level of theory with only the [CO,OH] well remaining. An exploration of this effect indicates that electron correlation is critically important and that DFT approaches incorrectly handle the internal hydrogen bonding in these molecules, thereby over-delocalizing the charges on the amino acid ligands. 

Block copolymers at homopolymer interfaces are poised to play a critical role in the compatibilization of mixed plastic waste, an area of growing importance as the rate of plastic accumulation rapidly increases. Using molecular dynamics simulations of Kremer–Grest polymer chains, we have investigated how the number of blocks and block degree of polymerization in a linear multiblock copolymer impacts the interface thermodynamics of strongly segregated homopolymer blends, which is key to effective compatibilization. The second virial coefficient reveals that interface thermodynamics are more sensitive to block degree of polymerization than to the number of blocks. Moreover, we identify a strong correlation between surface pressure (reduction of interfacial tension) and the spatial uniformity of block junctions on the interface, yielding a morphological framework for interpreting the role of compatibilizer architecture (number of blocks) and block degree of polymerization. These results imply that, especially at high interfacial loading, the choice of architecture of a linear multiblock copolymer compatibilizing surfactant does not greatly affect the modification of interfacial tension. 

In September 2017, Hurricane Irma made landfall in South Florida, causing a great deal of damage to mangrove forests along the southwest coast. A combination of hurricane strength winds and high storm surge across the area resulted in canopy defoliation, broken branches, and downed trees. Evaluating changes in mangrove forest structure is significant, as a loss or change in mangrove forest structure can lead to loss in the ecosystems services that they provide. In this study, we used lidar remote sensing technology and field data to assess damage to the South Florida mangrove forests from Hurricane Irma. Lidar data provided an opportunity to investigate changes in mangrove forests using 3D high-resolution data to assess hurricane-induced changes at different tree structure levels. Using lidar data in conjunction with field observations, we were able to model aboveground necromass (AGN; standing dead trees) on a regional scale across the Shark River and Harney River within Everglades National Park. AGN estimates were higher in the mouth and downstream section of Shark River and higher in the downstream section of the Harney River, with higher impact observed in Shark River. Mean AGN estimates were 46 Mg/ha in Shark River and 38 Mg/ha in Harney River and an average loss of 29% in biomass, showing a significant damage when compared to other areas impacted by Hurricane Irma and previous disturbances in our study region.