Catalytic hydrolysis of phosphate esters in microemulsions

Garlick, Stephanie M.; Durst, H. D.; Mackay, Raymond A.; Haddaway, Keith G; Longo, Frederick R.

doi:10.1016/0021-9797(90)90021-f

Cited by 16 publications

(11 citation statements)

References 26 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…An effective reagent in the first regard is o-iodosobenzoic acid, [12][13][14]19,22,50 while aqueous perhydroxide ion has shown promise for the latter. 21 Yang et al 21 have demonstrated that aqueous perhydroxide ion reacts with VX 40 times faster than aqueous hydroxide ion.…”

Section: Introductionmentioning

confidence: 99%

Molecular orbital calculations on the P?S bond cleavage step in the hydroperoxidolysis of nerve agent VX

Patterson

Cramer

1998

J. Phys. Org. Chem.

View full text Add to dashboard Cite

The P-S bond cleavage process in the hydroperoxidolysis of a model system for the nerve agent VX was studied using ab initio and semiempirical molecular orbital methods. Aqueous solvation effects were included through single-point calculations using the semiempirical SM5.2PD/A continuum solvation model and geometries optimized at the HF/MIDI! level of theory. The predominant pathway for P-S bond cleavage involves pseudorotation of a low-energy trigonal bipyramidal intermediate followed by apical ligand ejection. In aqueous solution, the free energy barriers for these processes are found to be 14.3 and 4.6 kcal mol À1 , respectively, with electronic energies calculated at the MP2/cc-pVDZ//HF/MIDI! level of theory. By comparison with another continuum model of solvation (PCM), it is concluded that the SM5.2PD/A model performs well even for hypervalent phosphorus species, in spite of not having included any such molecules in the model's parameterization set.

show abstract

Section: Introductionmentioning

confidence: 99%

Molecular orbital calculations on the P?S bond cleavage step in the hydroperoxidolysis of nerve agent VX

Patterson

Cramer

1998

J. Phys. Org. Chem.

View full text Add to dashboard Cite

show abstract

“…However, the oil dissolving power of microemulsions is greatly enhanced when long‐chain hydroxamic acids are employed as cosurfactants. Such systems are, therefore, very attractive as a microreactor for the hydrolytic reaction in cationic microemulsion . The rate upgrading of the octanohydroxamate ion on the cleavage of paraoxon may be discussed based on size of an oil pool (confirmed by DLS).…”

Section: Resultsmentioning

confidence: 99%

Hydrolytic Cleavage of Paraoxon by Octanohydroxamate Ion in Cationic Microemulsions

Satnami

Dewangan

Nagwanshi³

2016

Int J of Chemical Kinetics

View full text Add to dashboard Cite

The hydrolysis reaction of O,O‐diethyl O‐p‐nitrophenylphosphate (Paraoxon) with the octanohydroxamate ion (OHA−) was studied in a cationic oil‐in‐water (O/W) microemulsion system over a pH range 7.5–12.0 at 300 K. The O/W systems are stabilized by using cationic surfactant, cetyltrimethylammonium bromide (CTAB), and n‐butanol as cosurfactants. In a microemulsion, the rate enhancement by OHA− is greater toward the cleavage of paraoxon than its spontaneous (2.1 × 107 s−1) hydrolysis. The kobs values for the reaction of paraoxon with OHA− were determined in different microemulsion compositions with varying chain length of alcohols (n‐butanol, n‐pentanol, n‐octanol, and n‐dodecanol) and alkanes (n‐hexane, n‐heptane, and n‐decane). The effects of water content, pH, and size of the oil pool have been discussed.

show abstract

“…It is noted that the use of micelle‐forming surfactant can partly help the solubilization of OP compound in water which are often sparingly soluble. That is why, in a similar mechanism to micellar system, micro emulsion was also tried as media for IBA‐catalyzed PNPDPP hydrolysis . Various solvents and surface active components together with IBA derivatives were tested for optimum hydrolysis rate.…”

Section: Other Nanomaterials For Mimicking Phosphatases and Nucleasesmentioning

confidence: 99%

From DNA to Nerve Agents – The Biomimetic Catalysts for the Hydrolysis of Phosphate Esters

et al. 2020

View full text Add to dashboard Cite

The phosphate ester bonds are widely present in living organisms and in the environment. From the nucleic acids to the sparingly dispersed pesticides and chemical warfare residues, the phosphoester bond's stability against hydrolysis can be extremely high or exceptionally low. Recently, the enzyme-mimicking nanomaterials, namely 'nanozyme', have been explored for their activities in hydrolytically cleaving DNA, organophosphate and their analogues. Herein in a broad perspective these nanomaterials were summarized and compared with a view to reproducing the catalysis efficiency and selectivity of natural phosphatases and nucleases. The development of biomimetic inorganic materials would not only provide potential nanomedicine for future gene editing, but also offer alternative solutions to the environmentally friendly treatment of pesticide residues and chemical warfare stockpiles.

show abstract

Catalytic hydrolysis of phosphate esters in microemulsions

Cited by 16 publications

References 26 publications

Molecular orbital calculations on the P?S bond cleavage step in the hydroperoxidolysis of nerve agent VX

Molecular orbital calculations on the P?S bond cleavage step in the hydroperoxidolysis of nerve agent VX

Hydrolytic Cleavage of Paraoxon by Octanohydroxamate Ion in Cationic Microemulsions

From DNA to Nerve Agents – The Biomimetic Catalysts for the Hydrolysis of Phosphate Esters

Contact Info

Product

Resources

About