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  • Enhanced Reactivity of Aluminum Complexes Containing P-Bridged Biphenolate Ligands in Ring-Opening Polymerization Catalysis

    Zou, Xue-Ru; Chang, Yu-Ning; Huang, Kuo-Wei; Liang, Lan-Chang (Frontiers Media SA, 2018-12-13)
    Aluminum complexes containing [RP(O)(2-O-3,5-tBu2C6H2)2]2− [R = tBu (3a), Ph (3b)] have been synthesized, structurally characterized, and their reactivity studied in comparison with those of their [RP(2-O-3,5-tBu2C6H2)2]2− [R = tBu (2a), Ph (2b)] analogs. Treating AlMe3 with one equiv of H2[3a-b] in THF at 0°C affords quantitatively [3a-b]AlMe, subsequent reactions of which with benzyl alcohol in THF at 25°C generate {[3a-b]Al(μ2-OCH2Ph)}2. The methyl [3a-b]AlMe and the benzyloxide {[3a-b]Al(μ2-OCH2Ph)}2 are all active for catalytic ring-opening polymerization (ROP) of ε-caprolactone and rac-lactide (rac-LA). Controlled experiments reveal that {[3a]Al(μ2-OCH2Ph)}2 is competent in living polymerization. Kinetic studies indicate that [3a]AlMe, in the presence of benzyl alcohol, catalyzes ROP of rac-LA at a rate faster than [3b]AlMe and [2a]AlMe(THF) by a factor of 1.8 and 23.6, respectively, highlighting the profound reactivity enhancement in ROP catalysis by varying the P-substituents of these biphenolate complexes of aluminum.
  • Remobilization of Heavy Metals by Mangrove Leaves

    Almahasheer, Hanan; Serrano, Oscar; Duarte, Carlos M.; Irigoien, Xabier (Frontiers Media SA, 2018-12-13)
    Several studies have been carried out on heavy metal pollution in mangrove ecosystems. However, the role of mangroves in heavy metal remobilization is still relatively unknown. On one side, mangrove woody organs and soils sequester heavy metals for long time periods, but on the other hand, senescence of mangrove leaves may return these metals collected by roots to the upper layers of the soil. Here, we analyzed the concentration of chemical elements (Al, As, Cd, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Sr, V, and Zn) as a function of age in mangrove leaves to understand heavy metals retention by the plant and to quantify the amounts shed with senescing leaves. In addition, we estimated metal concentrations and stocks in mangrove soils. Our results revealed that the concentration of most metals increased with leaf age, resulting in the remobilization of metals stored in soil, thereby returning metals to the upper layers of the soil during senescence of mangrove leaves. Only Cu was reabsorbed prior to shedding of leaves, a mechanism similar to that described for nutrients in mangroves globally. These results provide key data to understand mangroves role in the dynamics of heavy metals.
  • Multiscale and Multimodal Analysis for Computational Biology

    Gao, Xin; Chen, Jake Y.; Zaki, Mohammed J. (Institute of Electrical and Electronics Engineers (IEEE), 2018-12-13)
    The papers in this special section were presented at the 16th International Workshop on Data Mining in Bioinformatics (BIOKDD17). The BIOKDD17 Workshop was organized in conjunction with the ACM SIGKDD International Conference on Knowledge Discovery and Data Mining on August 14, 2017 in Halifax, Canada. It brought together international researchers in the interacting disciplines of data mining, medical informatics, and bioinformatics at the World Trade and Convention Centre venue. The goal of this workshop is to encourage Knowledge Discovery and Data mining (KDD) researchers to take on the numerous challenges that bioinformatics offers. Bioinformatics is the science of managing, mining, and interpreting information from biological data. Various genome projects have contributed to an exponential growth in DNA and protein sequence databases. Rapid advances in high-throughput technologies, such as microarrays, mass spectrometry, and new/next-generation sequencing, can monitor quantitatively the presence or activity of thousands of genes, RNAs, proteins, metabolites, and compounds in a given biological state. The ongoing influx of these data, the pressing need to address complex biomedical challenges, and the gap between the two have collectively created exciting opportunities for data mining researchers.
  • Intra-Season Crop Height Variability at Commercial Farm Scales Using a Fixed-Wing UAV

    Ziliani, Matteo; Parkes, Stephen; Hoteit, Ibrahim; McCabe, Matthew (MDPI AG, 2018-12-12)
    Monitoring the development of vegetation height through time provides a key indicator of crop health and overall condition. Traditional manual approaches for monitoring crop height are generally time consuming, labor intensive and impractical for large-scale operations. Dynamic crop heights collected through the season allow for the identification of within-field problems at critical stages of the growth cycle, providing a mechanism for remedial action to be taken against end of season yield losses. With advances in unmanned aerial vehicle (UAV) technologies, routine monitoring of height is now feasible at any time throughout the growth cycle. To demonstrate this capability, five digital surface maps (DSM) were reconstructed from high-resolution RGB imagery collected over a field of maize during the course of a single growing season. The UAV retrievals were compared against LiDAR scans for the purpose of evaluating the derived point clouds capacity to capture ground surface variability and spatially variable crop height. A strong correlation was observed between structure-from-motion (SfM) derived heights and pixel-to-pixel comparison against LiDAR scan data for the intra-season bare-ground surface (R2 = 0.77 − 0.99, rRMSE = 0.44% − 0.85%), while there was reasonable agreement between canopy comparisons (R2 = 0.57 − 0.65, rRMSE = 37% − 50%). To examine the effect of resolution on retrieval accuracy and processing time, an evaluation of several ground sampling distances (GSD) was also performed. Our results indicate that a 10 cm resolution retrieval delivers a reliable product that provides a compromise between computational cost and spatial fidelity. Overall, UAV retrievals were able to accurately reproduce the observed spatial variability of crop heights within the maize field through the growing season and provide a valuable source of information with which to inform precision agricultural management in an operational context.
  • Thermal cooling to improve hydraulic fracturing efficiency and hydrocarbon production in shales

    Enayatpour, Saeid; van Oort, Eric; Patzek, Tadeusz (Elsevier BV, 2018-12-12)
    Unconventional hydrocarbon reserves contained in oil and gas shale formations are proving themselves to be abundant sources of current and future energy supply, unlocked through the technologies of horizontal drilling and hydraulic fracturing. Despite the various technology improvements that have buoyed the ”shale revolution” in the last decade, there remain very significant opportunities to further improve hydrocarbon recovery from shales by making hydraulic fracturing more efficient. In this paper, we look into the possibility of stimulating a rock matrix to a higher degree with hydraulic fractures by deliberately cooling down the rock. Cooling reduces in-situ thermal stress, which lowers initiation and propagation pressures of hydraulic fractures. Moreover, when a laterally confined solid undergoes temperature reduction induced by cooling, a thermal stress gradient is developed in the solid body. We perform sensitivity analyses to show that in an in-homogenous shale, this thermal stress gradient can lead to differential contraction of its various mineralogical constituents, which in turn may create thermal cracks. The opening of such cracks increases shale permeability and provides additional pathways for the flow of hydrocarbons, thereby enhancing productivity. Here, we solve the coupled equations of stress, heat transfer and flow using finite element techniques for hydraulic stimulation amplified by cooling. It is shown that thermal cracks in tight formations induced by thermal cooling have the potential to improve the productivity of horizontal wellbores placed in shale by an estimated 16% for the case of methane gas flow through thermally stimulated shale of micro-darcy permeability.

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