Redox manipulations

T0586 Pacific Northwest National Laboratory, In Sim Redox Manipulation T0588 Pacific Northwest National Laboratory, Self-Assembled Mesoporous Support (SAMMS) Technology... 

T0586 Pacific Northwest National Laboratory, In Situ Redox Manipulation T0600 Perma-Fix Environmental Services, Inc., Perma-Fix Process T0601 Permeable Reactive Barriers (PRBs)—General T0606 PHYTOKinetics, Inc., Phytoremediation T0607 Phytoremediation—General... 

T0586 Pacific Northwest National Laboratory, In Situ Redox Manipulation... 

In situ redox manipulation (ISRM) is an in situ, groundwater remediation technology for manipulating the oxidation-reduction (redox) potential of an unconfined aquifer to immobilize inorganic contaminants (metals, inorganic ions, and radionuclides) and to destroy organic contaminants (primarily chlorinated hydrocarbons). 

TABLE 1 Comparison of Estimated Costs of In Situ Redox Manipulation (ISRM) versus Pump-and-Treat Technoiogy... 

It may be difficult to imagine the alkylation of a 3,5-dialkoxyphenylcarbanion in which no ortho chelators are available to assist deprotonation at the desired position, not to mention the disjoint relationship of this donor carbon to the oxy substituents present. A solution to this problem is provided by redox manipulations and incorporation of a removable acceptor group to affirm the donor site. Thus, the Birch reduction product of 3,5-dimethoxybenzoic acid readily undergoes alkylation, and oxidative decarboxylation generates the aromatic compound [273]. 

Fruchter, J.S., J.E. Amonette, C.R. Cole, Y.A. Corby, M.D. Humphrey, J.D. Istok, F.A. Spane, J.E. Szecsody, S.S. Teel, V.R. Vermeul, M.D. Williams, and S.B. Yabusaki. 1996. In Situ Redox Manipulation Field Injection Test Report - Hanford 100-H Area, Pacific Northwest National Laboratory, PNNL-11372, UC-602. 

Fruchter JS, Cole CR, Williams MD, Vermeul VR, Amonette JE, Szecsody JE, Istok JD, Flumphrey MD. Creation of a subsurface permeable treatment zone for aqueous chromate contamination using in situ redox manipulation. Ground Water Monit Remediat 2000 20 66-77. 

Istok JD, Amonette JE, Cole CR, Fruchter JS, Flumphrey MD, Szecsody JE, Teel SS, Vermeul VR, Williams MD, Yabusaki SB. In situ redox manipulation by dithionite injection intermediate-scale laboratory experiments. Ground Water 1999 37 884-889. 

Injection of a reductant such as sodium dithionite creates a reducing zone that may be effective in immobilizing uranium and other redox-active radionuclides. The technique is known as in situ redox manipulation (ISRM). It has been shown to be moderately effective for chromium and is proposed for use at the Hanford site for remediation of a uranium groundwater plume (Fmchter et al., 1996). 

Fmchter J. S., Amonette J. E., Cole C. R., Gorby Y. A., Humphrey M. D., Istok J. D., Olsen K. B., Spane E. A., Szecsody J. E., Teel S. S., Vermeul V. R., Williams M. D., and Yabusaki S. B. (1996) In situ redox manipulation field injection test report—Hanford 100 H area. Pacific Northwest National Laboratory. 

Williams, M. D. Yabusaki, S. B. In Situ Redox Manipulation Field Injection Test Report - Hanford 100-H Area, Pacific Northwest National Laboratory, 1996. 

Fuchs JE, Huber RG, Von Grafenstein S, Wallnoefer HG, Spitzer GM, Euchs D, Liedl KR (2012) Dynamic regulation of phenylalanine hydroxylase by simulated redox manipulation. PloS One 7(12) e53005. doi 10.1371/joumal.pone.0053005... 

SCHEME 12 Redox manipulations for the reductive opening of epoxide 2. 

Although highly efficient, this transformation could not be further elaborated to the natural kadangustin (192) and a different approach was developed. Thus, the tertiary alcohol 222 was first prepared by the addition of lithiate 211 to the common precursor 206 (Scheme 10.42), and the subsequent reductive deoxygenation and the redox manipulation to the terminal double bond completed the total synthesis of enantiomer of the natural (+)-kadangustin J (192) [74b]. 

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