Homosexuality and the Use of Reproductive Technology

General Education Centr

The Role of Antecedent Groundwater Heads in Controlling Transient Aquifer Storage and Flood Peak Attenuation in Karst Watersheds

Transient storage of floodwaters in aquifers is known to attenuate peak flows in rivers and drive subsurface dissolution. Transient aquifer storage could be enhanced in watersheds overlying karst aquifers where caves facilitate surface and groundwater exchange. Few studies, however, have examined controls on, or magnitudes of, transient aquifer storage or flood peak attenuation in karstic watersheds. Here we evaluate flood peak attenuation with multiple linear regression analyses of 10 years of river and groundwater data from the Suwannee River, which flows over the karstic upper Floridan aquifer in north‐central Florida and experiences frequent flooding. Regressions show antecedent river stage exerts the dominant control on magnitudes of transient aquifer storage, with recharge and time to peak having secondary controls. Specifically, low antecedent stages result in larger magnitudes of transient aquifer storage and thus greater flood attenuation than conditions of elevated antecedent stage. These findings suggest subsurface weathering, including cave formation and enlargement, caused by transient aquifer storage could occur on a more frequent basis in aquifers where groundwater table elevation is lowered due to anthropogenic or climatic influences. Our work also shows that measures of groundwater table elevation prior to an event could be used to improve predictive flood models

Metallaphotoredox-catalysed <i>sp</i>³–<i>sp</i>³ cross-coupling of carboxylic acids with alkyl halides

In the past 50 years, cross-coupling reactions mediated by transition metals have changed the way in which complex organic molecules are synthesized. The predictable and chemoselective nature of these transformations has led to their widespread adoption across many areas of chemical research1. However, the construction of a bond between two sp3-hybridized carbon atoms, a fundamental unit of organic chemistry, remains an important yet elusive objective for engineering cross-coupling reactions2. In comparison to related procedures with sp2-hybridized species, the development of methods for sp3–sp3 bond formation via transition metal catalysis has been hampered historically by deleterious side-reactions, such as β-hydride elimination with palladium catalysis or the reluctance of alkyl halides to undergo oxidative addition3,4. To address this issue, nickel-catalysed cross-coupling processes can be used to form sp3–sp3 bonds that utilize organometallic nucleophiles and alkyl electrophiles5,6,7. In particular, the coupling of alkyl halides with pre-generated organozinc8,9, Grignard10 and organoborane11 species has been used to furnish diverse molecular structures. However, the manipulations required to produce these activated structures is inefficient, leading to poor step- and atom-economies. Moreover, the operational difficulties associated with making and using these reactive coupling partners, and preserving them through a synthetic sequence, has hindered their widespread adoption. A generically useful sp3–sp3 coupling technology that uses bench-stable, native organic functional groups, without the need for pre-functionalization or substrate derivatization, would therefore be valuable. Here we demonstrate that the synergistic merger of photoredox and nickel catalysis enables the direct formation of sp3–sp3 bonds using only simple carboxylic acids and alkyl halides as the nucleophilic and electrophilic coupling partners, respectively. This metallaphotoredox protocol is suitable for many primary and secondary carboxylic acids. The merit of this coupling strategy is illustrated by the synthesis of the pharmaceutical tirofiban in four steps from commercially available starting materials