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Diethyl Phosphate (diethyl + phosphate)
Selected AbstractsA Time-Resolved Spectroscopic Study of the Bichromophoric Phototrigger 3,,5,-Dimethoxybenzoin Diethyl Phosphate: Interaction Between the Two Chromophores Determines the Reaction PathwayCHEMISTRY - A EUROPEAN JOURNAL, Issue 17 2010Chensheng Ma Dr. Abstract 3,,5,-Dimethoxybenzoin (DMB) is a bichromophoric system that has widespread application as a highly efficient photoremovable protecting group (PRPG) for the release of diverse functional groups. The photodeprotection of DMB phototriggers is remarkably clean, and is accompanied by the formation of a biologically benign cyclization product, 3,,5,-dimethoxybenzofuran (DMBF). The underlying mechanism of the DMB deprotection and cyclization has, however, until now remained unclear. Femtosecond transient absorption (fs-TA) spectroscopy and nanosecond time-resolved resonance Raman (ns-TR3) spectroscopy were employed to detect the transient species directly, and examine the dynamic transformations involved in the primary photoreactions for DMB diethyl phosphate (DMBDP) in acetonitrile (CH3CN). To assess the electronic character and the role played by the individual sub-chromophore, that is, the benzoyl, and the di- meta -methoxybenzylic moieties, for the DMBDP deprotection, comparative fs-TA measurements were also carried out for the reference compounds diethyl phosphate acetophenone (DPAP), and 3,,5,-dimethoxybenzylic diethyl phosphate (DMBnDP) in the same solvent. Comparison of the fs-TA spectra reveals that the photoexcited DMBDP exhibits distinctly different spectral character and dynamic evolution from those of the reference compounds. This fact, combined with the related steady-state spectral and density functional theoretical results, strongly suggests the presence in DMBDP of a significant interaction between the two sub-chromophores, and that this interaction plays a governing role in determining the nature of the photoexcitation and the reaction channel of the subsequent photophysical and photochemical transformations. The ns-TR3 results and their correlation with the fs-TA spectra and dynamics provide evidence for a novel concerted deprotection,cyclization mechanism for DMBDP in CH3CN. By monitoring the direct generation of the transient DMBF product, the cyclization time constant was determined unequivocally to be ,1,ns. This indicates that there is little relevance for the long-lived intermediates (>10,ns) in giving the DMBF product, and excludes the stepwise mechanism proposed in the literature as the major pathway for the DMB cyclization reaction. This work provides important new insights into the origin of the 3,,5,-dimethoxy substitution effect for the DMB photodeprotection. It also helps to clarify the many different views presented in previous mechanistic studies of the DMB PRPGs. In addition to this, our fs-TA results on the reference compound DMBnDP in CH3CN provide the first direct observation (to the best of our knowledge) showing the predominance of a prompt (,2,ps) heterolytic bond cleavage after photoexcitation of meta -methoxybenzylic compounds. This provides insight into the long-term controversies about the photoinitiated dissociation mode of related substituted benzylic compounds. [source] Metabolism of chlorpyrifos and chlorpyrifos oxon by human hepatocytes,JOURNAL OF BIOCHEMICAL AND MOLECULAR TOXICOLOGY, Issue 6 2006Kyoungju Choi Abstract The metabolism of chlorpyrifos (CPS) and chlorpyrifos oxon (CPO) by human hepatocytes and human liver S9 fractions was investigated using LC-MS/MS. Cytochrome P450 (CYP)-dependent and phase II-related products were determined following incubation with CPS and CPO. CYP-related products, 3,5,6-trichloro-2-pyridinol (TCP), diethyl thiophosphate, and dealkylated CPS, were found following CPS treatment and dealkylated CPO following CPO treatment. Diethyl phosphate was not identified because of its high polarity and lack of retention with the chromatographic conditions employed. Phase II-related conjugates, including O- and S-glucuronides as well as 11 GSH-derived metabolites, were identified in CPS-treated human hepatocytes, although the O -sulfate of TCP conjugate was found only when human liver S9 fractions were used as the enzyme source. O -Glucuronide of TCP was also identified in CPO-treated hepatocytes. CPS and CPO were identified using HPLC,UV after CPS metabolism by the human liver S9 fraction. However, CPO was not found following treatment of human hepatocytes with either CPS or CPO. These results suggest that human liver plays an important role in detoxification, rather than activation, of CPS. © 2006 Wiley Periodicals, Inc. J Biochem Mol Toxicol 20:279,291, 2006; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/jbt.20145 [source] Effect of the Molecular Size of Analytes on Polydiacetylene ChromismADVANCED FUNCTIONAL MATERIALS, Issue 9 2010Donghwan Seo Abstract The pH chromism of polydiacetylenes (PDAs) is examined with respect to the molecular size and acidity of acid analytes, along with the alkyl spacer length of primary-amine-functionalized diacetylene (DA) lipids. pH turns out to be an important parameter to charge amine headgroups of PDA but a change in pH does not necessarily result in a PDA color change. The molecular size of acid analytes is identified as another factor that can produce a configurational change in PDA amine headgroups, followed by perturbation of the ene,yne conjugated backbone. In addition, the length of a flexible alkyl spacer between the amine headgroup and the amide group of the diacetylene lipids is found to strongly affect the degree of PDA chromatic transition. The longer alkyl spacer shows a smaller chromatic transition from blue to red phase. The alkyl spacer seems to provide a certain degree of freedom to the amine headgroup, thus decreasing the transfer of headgroup steric effects to the PDA backbone. These correlations found for PDA chromism are applied to the development of a system that colorimetrically detects diethyl phosphate (DEP), a degraded nerve agent simulant. PDA liposomes show a selective chromatic transition upon binding with DEP compared to other acid analytes. [source] Practical Iron-Catalyzed Allylations of Aryl Grignard ReagentsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 13 2010Matthias Mayer Abstract An operationally simple iron-catalyzed reductive cross-coupling reaction between aryl halides and allyl electrophiles has been developed. The underlying domino process exhibits high versatility with respect to the allylic leaving group (acetate, tosylate, diethyl phosphate, methyl carbonate, trimethylsilanolate, methanethiolate, chloride, bromide) and high economic and environmental sustainability with respect to the catalyst system (0.2,5 mol% tris(acetylacetonato)iron(III), ligand-free) and reaction conditions (tetrahydrofuran, 0,°C, 45,min). [source] Molecular dynamics simulations of the detoxification of paraoxon catalyzed by phosphotriesteraseJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 15 2009Xin Zhang Abstract Combined QM(PM3)/MM molecular dynamics simulations together with QM(DFT)/MM optimizations for key configurations have been performed to elucidate the enzymatic catalysis mechanism on the detoxification of paraoxon by phosphotriesterase (PTE). In the simulations, the PM3 parameters for the phosphorous atom were reoptimized. The equilibrated configuration of the enzyme/substrate complex showed that paraoxon can strongly bind to the more solvent-exposed metal ion Zn,, but the free energy profile along the binding path demonstrated that the binding is thermodynamically unfavorable. This explains why the crystal structures of PTE with substrate analogues often exhibit long distances between the phosphoral oxygen and Zn,. The subsequent SN2 reaction plays the key role in the whole process, but controversies exist over the identity of the nucleophilic species, which could be either a hydroxide ion terminally coordinated to Zn, or the ,-hydroxo bridge between the ,- and ,-metals. Our simulations supported the latter and showed that the rate-limiting step is the distortion of the bound paraoxon to approach the bridging hydroxide. After this preparation step, the bridging hydroxide ion attacks the phosphorous center and replaces the diethyl phosphate with a low barrier. Thus, a plausible way to engineer PTE with enhanced catalytic activity is to stabilize the deformed paraoxon. Conformational analyses indicate that Trp131 is the closest residue to the phosphoryl oxygen, and mutations to Arg or Gln or even Lys, which can shorten the hydrogen bond distance with the phosphoryl oxygen, could potentially lead to a mutant with enhanced activity for the detoxification of organophosphates. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2009 [source] A Time-Resolved Spectroscopic Study of the Bichromophoric Phototrigger 3,,5,-Dimethoxybenzoin Diethyl Phosphate: Interaction Between the Two Chromophores Determines the Reaction PathwayCHEMISTRY - A EUROPEAN JOURNAL, Issue 17 2010Chensheng Ma Dr. Abstract 3,,5,-Dimethoxybenzoin (DMB) is a bichromophoric system that has widespread application as a highly efficient photoremovable protecting group (PRPG) for the release of diverse functional groups. The photodeprotection of DMB phototriggers is remarkably clean, and is accompanied by the formation of a biologically benign cyclization product, 3,,5,-dimethoxybenzofuran (DMBF). The underlying mechanism of the DMB deprotection and cyclization has, however, until now remained unclear. Femtosecond transient absorption (fs-TA) spectroscopy and nanosecond time-resolved resonance Raman (ns-TR3) spectroscopy were employed to detect the transient species directly, and examine the dynamic transformations involved in the primary photoreactions for DMB diethyl phosphate (DMBDP) in acetonitrile (CH3CN). To assess the electronic character and the role played by the individual sub-chromophore, that is, the benzoyl, and the di- meta -methoxybenzylic moieties, for the DMBDP deprotection, comparative fs-TA measurements were also carried out for the reference compounds diethyl phosphate acetophenone (DPAP), and 3,,5,-dimethoxybenzylic diethyl phosphate (DMBnDP) in the same solvent. Comparison of the fs-TA spectra reveals that the photoexcited DMBDP exhibits distinctly different spectral character and dynamic evolution from those of the reference compounds. This fact, combined with the related steady-state spectral and density functional theoretical results, strongly suggests the presence in DMBDP of a significant interaction between the two sub-chromophores, and that this interaction plays a governing role in determining the nature of the photoexcitation and the reaction channel of the subsequent photophysical and photochemical transformations. The ns-TR3 results and their correlation with the fs-TA spectra and dynamics provide evidence for a novel concerted deprotection,cyclization mechanism for DMBDP in CH3CN. By monitoring the direct generation of the transient DMBF product, the cyclization time constant was determined unequivocally to be ,1,ns. This indicates that there is little relevance for the long-lived intermediates (>10,ns) in giving the DMBF product, and excludes the stepwise mechanism proposed in the literature as the major pathway for the DMB cyclization reaction. This work provides important new insights into the origin of the 3,,5,-dimethoxy substitution effect for the DMB photodeprotection. It also helps to clarify the many different views presented in previous mechanistic studies of the DMB PRPGs. In addition to this, our fs-TA results on the reference compound DMBnDP in CH3CN provide the first direct observation (to the best of our knowledge) showing the predominance of a prompt (,2,ps) heterolytic bond cleavage after photoexcitation of meta -methoxybenzylic compounds. This provides insight into the long-term controversies about the photoinitiated dissociation mode of related substituted benzylic compounds. [source] | ||||||||||