The photodissociation of benzoin diethyl phosphate (1, “caged” phosphate) was studied by nanosecond and picosecond laser flash photolysis. The lowest triplet state of 1, 31, was identified as the reactive excited state with an absorption maximum around 340 nm and a lifetime of 10-25 ns, depending on the solvent. Two different reaction paths were identified, both of which involve the release of ...

A new two-dimensional manganese(II) coordination polymer, [Mn(μ-DEP)(μ-Cl)(H2O)2]n (1) (DEP is diethyl phosphate), was prepared from the reaction of MnCl2.4H2O and TEP (TEP is triethyl phosphate) ligand in mixture of H2O/CH3OH (1:10) at 40 °C. Suitable crystals of this complex for crystal structure determination were obtained by slow evaporation of the produced colorless solution at room temper...

Af-Hydroxy-2-acetylaminofluorene was rapidly deacetylated by guinea pig liver and, to a lesser extent, by other guinea pig tissues examined. The enzyme activity was located in the microsomal fraction of the liver. The enzyme appeared to be stimulated by trisodium pentacyanoamine ferrate, and it was inhibited by SKF-525A (|3-diethylaminoethyldiphenylpropyl acetate hydrochloride), by sodium fluor...

The serine protease inhibitors diethyl p-nitrophenyl phosphate and phenylmethylsulfonyl fluoride (chemical modifiers of serine residue) and N-acetyl-l-tryptophan ethyl ester (competitive inhibitor of chymotryptic protease) inhibited 1-O-alkyl-2-acetyl-sn-glycero-3-phosphocholine (AGEPC; platelet-activating factor)-induced platelet aggregation and secretion. The inhibition was dependent on the p...

Five alkynyl phosphate esters have been synthesized as probes of the active site structure of phosphotriesterase. These compounds have the potential to be converted by the enzyme to a highly reactive ketene intermediate which can then react with an active site nucleophile causing irreversible inhibition of the enzyme by formation of an inactive covalent adduct. All five compounds completely ina...

In vitro metabolism of T-2 toxin with S-9 fraction obtained from livers of phenobarbital-treated pigs and rats in the presence of different esterase inhibitors, including NaF, p-hydroxymercuribenzoate, phenylmethylsulfonyl fluoride, eserine sulfate, diisopropylfluorophosphate, and diethyl p-nitrophenyl phosphate, was studied. The metabolism was completely shifted to the hydroxylation at the C-3...

We have developed a new photoremovable protecting group for caging phosphates in the near UV. Diethyl 2-(4-hydroxy-1-naphthyl)-2-oxoethyl phosphate (14a) quantitatively releases diethyl phosphate upon irradiation in aq MeOH or aq MeCN at 350 nm, with quantum efficiencies ranging from 0.021 to 0.067 depending on the solvent composition. The deprotection reactions originate from the triplet excit...

The primary and secondary 18O isotope effects for the alkaline (KOH) and enzymatic (phosphotriesterase) hydrolysis of two phosphotriesters, O,O-diethyl p-nitrophenyl phosphate (I) and O,O-diethyl O-(4-carbamoylphenyl) phosphate (II), are consistent with an associative mechanism with significant changes in bond order to both the phosphoryl and phenolic leaving group oxygens in the transition sta...