Stereochemical Study of Phosphonothioate Cleavage by a Metallomicelle

Moss, Robert A.; Gong, Paul K.; Morales‐Rojas, Hugo

doi:10.1021/ol0200394

Cited by 15 publications

(10 citation statements)

References 28 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…1,2 Assemblies of metal-chelating surfactants have been utilized in a variety of fields such as catalysis, 3,4 environmental remediation of toxic metals, 5,6 and magnetic resonance imaging contrast agents. 7 Some metal chelating surfactants undergo a change in aggregate morphology upon metal coordination.…”

Section: Introductionmentioning

confidence: 99%

XAS Study of a Metal-Induced Phase Transition by a Microbial Surfactant

2008

View full text Add to dashboard Cite

The metal-induced micelle-to-vesicle phase change that the ferric complex of the microbially produced amphiphile, marinobactin E (M E ), undergoes has been investigated by X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). Marinobactin E is one member of the suite of siderophores, marinobactins A-E, that are used by the source bacterium to facilitate iron acquisition. Fe(III)-M E undergoes a micelle-to-multilamellar vesicle transition in the presence of Cd(II) and Zn(II). XRD measurements indicate the interlamellar repeat distance of the Cd(II)-and Zn-(II)-induced multilamellar vesicles is ~5.3 nm. XAS spectra of the sedimented Cd(II)-and Zn(II)-induced multilamellar vesicles suggests hexadentate coordination of Cd(II) and Zn(II) consisting of two monodentate carboxylate ligands and four water ligands. This coordination environment supports the hypothesis that Cd(II) and Zn(II) bridge the terminal carboxylate moiety of two Fe(III)-M E headgroups, pulling the headgroups together in an arrangement that favors vesicle formation over the formation of micelles. XAS spectra of the Fe(III) center in the sedimented Cd(II)-and Zn(II)-induced vesicles confirm the anticipated six-coordinate geometry of Fe(III) by the M E headgroup via the two hydroxamate groups and the α-hydroxy amide moiety.

show abstract

Section: Introductionmentioning

confidence: 99%

XAS Study of a Metal-Induced Phase Transition by a Microbial Surfactant

2008

View full text Add to dashboard Cite

show abstract

“…MeParat b OMe OMe 122.36 11118.95 11118.45 11122.90 11118.42 11118.90 1110.67 8 (Hernandez et al, 2004); (d) Gifkins & Jacobson (1980); (e) R 2 = -NHC(CH 2 )Np (Np is naphthalene; Moss et al, 2002).…”

Section: Tablementioning

confidence: 99%

Two organophosphorus pesticides: methyl parathion and dicapthon

Baughman

Hall

2014

Acta Crystallogr C

View full text Add to dashboard Cite

Structural studies performed in this laboratory of organophosphorus pesticides continue with these related compounds. The -NO2 groups of methyl parathion (systematic name: dimethyl 4-nitrophenyl phosphorothioate, C8H10NO5PS) and dicapthon (systematic name: 2-chloro-4-nitrophenyl dimethyl phosphorothioate, C8H9ClNO5PS) make dihedral angles of 10.67 (8) and 5.8 (1)°, respectively, with the planes of their attached rings, which accompanies angular distortion at the ring C atoms to which the -NO2 groups are attached. Similar distortions are observed at the C atom to which the thiophosphate groups are attached. Significant differences in distances and angles around the phenolic O, versus the -OMe groups, explain why it is the site of hydrolysis for these compounds. A comparison of a torsion angle involving the thiophosphate group and phenolic O atom with similar pesticide structures is given and indicates steric influences on that angle.

show abstract

“…These compounds are not only highly toxic but also highly persistent in the environment. A significant body of information on the effect of divalent [4][5][6] and trivalent [7][8][9][10] ions on the hydrolysis of diesters like DNA and RNA has already been reported. Recent work has demonstrated extraordinary catalytic effect of tetravalent [11][12][13][14] cations on the hydrolysis of phosphate diester as well as nucleotides.…”

Section: Introductionmentioning

confidence: 99%

Tetravalent Metal Catalyzed Hydrolysis of Cyanofenphos: A Delayed Neurotoxic Organophosphorus Compound

Naik¹,

YADAV²,

CP³

2011

Int J of Chem Res

View full text Add to dashboard Cite

Abstract-Hydrolysis of O-ethyl O-p-cyanophenyl, phenyl phosphonothionate (Cyanofenphos) has been studied in the acidic medium with catalyst such as Zr 4+ , Ce 4+ , Hf 4+ and Th 4+ cations, and the rate maxima observed were at around pH 2.0. Since the metal aquo complex are known to exist in equilibrium with deprotonated species, and therefore metal bound OHnucleophile might be available abundantly even in acidic aqueous solutions. Thus an interaction of sulphur of P=S group with metal cation followed by an intramolecular nucleophilic attack of hydroxy anion at the ester phosphorus atom would results in the cleavage of P-O bond.

show abstract

Stereochemical Study of Phosphonothioate Cleavage by a Metallomicelle

Abstract: [reaction: see text] The copper metallomicellar hydrolysis of O-methyl O-4-nitrophenyl phenylphosphonothioate to O-methyl phenylphosphonothioic acid takes place with effectively complete inversion at phosphorus.

Cited by 15 publications

References 28 publications

XAS Study of a Metal-Induced Phase Transition by a Microbial Surfactant

XAS Study of a Metal-Induced Phase Transition by a Microbial Surfactant

Two organophosphorus pesticides: methyl parathion and dicapthon

Tetravalent Metal Catalyzed Hydrolysis of Cyanofenphos: A Delayed Neurotoxic Organophosphorus Compound

Contact Info

Product

Resources

About