- Rhodium-catalyzed phosphorylation reaction of water-soluble disulfides using hypodiphosphoric acid tetraalkyl esters in water
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RhCl3 catalyzed the exchange reaction of disulfides and hypodiphosphoric acid tetraalkyl esters in water under homogeneous conditions, which indicated the hypodiphosphoric acid tetraalkyl esters to be novel and efficient phosphorylation reagent
- Arisawa, Mieko,Fukumoto, Kohei,Yamaguchi, Masahiko
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- Ionization of the PH Bond in Diethyl Phosphonate
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Diethyl phosphonate is oxidized by halogens in a reaction subject to general base catalysis when the halogen concentration is sufficiently high.Under these conditions the reaction is zero order in iodine or bromine and the Broensted exponent, β, is, contrary to earlier reports, about 0.7.When the halogen concentration is quite low, but still within the range of the spectrophotometric analysis used, a third-order rate law is obeyed and the product of the ionization constant of the phosphonate and the rate constant for the reaction of the anion with halogen (which is probably diffusion controlled) can be derived.This gives an acid dissociation constant of 2.5*10-15.When the diethyl phosphonate is exchanged with D2O, a substantial kinetic isotope effect is observed for the oxidation, again contrary to expectation from previous reports on a similar reaction.This reaction is thus closely analogous to the ionization of hydrogen α to a carbonyl group or a nitro group in all of which the proton transfer is slower than the diffusion-controlled rate in both directions.
- Lewis, Edward S.,Spears, L. Gene
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- Diethyl Isopropyl and Isopropenyl Phosphate via Differently Generated Ketyl Radicals of Acetone Reacting with Diethyl Phosphoric Acid
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Photochemically excited acetone reacts in 1,2-dimethoxy ethane with diethyl phosphoric acid to diethyl isopropyl phosphate.The same product is formed by reduction of acetone with magnesium amalgam in benzene in the presence of the same phosphoric acid derivative.Thermal decomposition of tetramethyldioxetane in benzene in the presence of diethyl phosphoric acid appears to yield primarily diethyl isopropenyl phosphate.
- Schole, Juergen,Schole, Christine,Eikemeyer, Juergen,Krebs, Hans Christoph
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- Synthesis and structure of complexes of phosphorus pentachloride with 4-dimethylaminopyridine and n-methylimidazole
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Complexes of phosphorus pentachloride with 4-dimethylaminopyridine and N-methylimidazole were synthesized. The molecular structure of the phosphorus pentachloride complex with N-methylimidazole was determined by single-crystal X-ray diffraction. In the cationic part of the complex, the phosphorus atom possesses four P - Cl bonds within the range 2.109-2.148 A and two cis-P-N bonds (1.811 and 1.832 A) with N-methylimidazole and exhibits slightly distorted octahedral coordination with angles at phosphorus atom in the range 87.57°-91.50°. The relative stability of the cis and trans conformations of the complex was studied by DFT calculations. The chemical properties and reactivity of the compounds obtained are determined; their utility as condensing agents in the synthesis of amides from acids and amines was shown.
- Pipko, Sergey E.,Bezgubenko, Ludmila V.,Sinitsa, Anatoliy D.,Rusanov, Eduard B.,Kapustin, Evgeniy G.,Povolotskii, Mark I.,Shvadchak, Volodymyr V.
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- Wireless Hazard Badges to Detect Nerve-Agent Simulants
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Human exposure to hazardous chemicals can have adverse short- and long-term health effects. In this Communication, we have developed a single-use wearable hazard badge that dosimetrically detects diethylchlorophosphate (DCP), a model organophosphorous cholinesterase inhibitor simulant. Improved chemically actuated resonant devices (CARDs) are fabricated in a single step and unambiguously relate changes in chemiresistance to a wireless readout. To provide selective and readily manufacturable sensor elements for this platform, we developed an ionic-liquid-mediated single walled carbon nanotube based chemidosimetric scheme with DCP limits of detection of 28 ppb. As a practical demonstration, an 8 h workday time weighted average equivalent exposure of 10 ppb DCP effects an irreversible change in smartphone readout.
- Zhu, Rong,Azzarelli, Joseph M.,Swager, Timothy M.
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- Broad-Spectrum Liquid- and Gas-Phase Decontamination of Chemical Warfare Agents by One-Dimensional Heteropolyniobates
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A wide range of chemical warfare agents and their simulants are catalytically decontaminated by a new one-dimensional polymeric polyniobate (P-PONb), K12[Ti2O2][GeNb12O40]?19 H2O (KGeNb) under mild conditions and in the dark. Uniquely, KGeNb facilitates hydrolysis of nerve agents Sarin (GB) and Soman (GD) (and their less reactive simulants, dimethyl methylphosphonate (DMMP)) as well as mustard (HD) in both liquid and gas phases at ambient temperature and in the absence of neutralizing bases or illumination. Three lines of evidence establish that KGeNb removes DMMP, and thus likely GB/GD, by general base catalysis: a) the k(H2O)/k(D2O) solvent isotope effect is 1.4; b) the rate law (hydrolysis at the same pH depends on the amount of P-PONb present); and c) hydroxide is far less active against the above simulants at the same pH than the P-PONbs themselves, a critical control experiment.
- Guo, Weiwei,Lv, Hongjin,Sullivan, Kevin P.,Gordon, Wesley O.,Balboa, Alex,Wagner, George W.,Musaev, Djamaladdin G.,Bacsa, John,Hill, Craig L.
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- Prodrugs of butyric acid. Novel derivatives possessing increased aqueous solubility and potential for treating cancer and blood diseases
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The synthesis and biological activities of acidic, basic and neutral types of butyric acid (BA) prodrugs possessing increased aqueous solubility are described. The compounds are butyroyloxyalkyl derivatives of carboxylic acids, which possess functionalities suitable for aqueous solubilization. The anticancer activity of the prodrugs in vitro was evaluated by examining their effect on the growth of human colon, breast and pancreatic carcinoma cell lines, and their solubility in aqueous media was determined. The most promising compounds, with respect to activity and solubility, were found to be the butyroyloxymethyl esters of glutaric 2a and nicotinic acids 4a and phosphoric acid as its diethyl ester 10a, which displayed IC50 values of 100 μM or lower. These prodrugs are expected to release formaldehyde upon metabolic hydrolysis. The corresponding butyroyloxyethyl esters (2b, 4b and 10b) that release acetaldehyde upon metabolism were significantly less potent. A similar correlation was observed for growth inhibition of the human prostate carcinoma cell lines PC-3 and LnCap and for induction of differentiation and apoptosis in the human myeloid leukemia cell line HL-60. The higher biological activity of the formaldehyde-releasing prodrugs 2a and 10a was further confirmed when induction of hemoglobin (Hb) synthesis in the human erythroleukemic cell line K562 was measured. Moreover, a therapeutic index (IC50/ED50) of ca. 5 was observed. The acute i.p. toxicity LD50 in mice for 2a, 2b, 10a and 10b was similar and in the range of 400-600 mg kg-1. The results obtained support the potential use of the butyric acid prodrugs for the treatment of neoplastic diseases and β-globin disorders.
- Nudelman, Abraham,Gnizi, Elisheva,Katz, Yifat,Azulai, Revital,Cohen-Ohana, Mirit,Zhuk, Regina,Sampson, Sanford R,Langzam, Leah,Fibach, Eitan,Prus, Eugenia,Pugach, Victoria,Rephaeli, Ada
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- Does phosphoryl protonation occurs in aqueous phosphoesters solutions
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Ionisation of trimethylphosphate (TMP), dimethylphosphate (DMP) and diethylphosphate (DEP) is investigated by acidic titration in water by Raman (R), Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopies. The vibrational frequencies of the PO2- ionic form and the neutral form were found in accord with the literature. While increasing further H+ concentration, the PO band disappears in the benefit of new ones. These results, together with deuteration experiments indicate the presence of a new ionic form positively charged with general formula R1R2R3P(OH)+ or R 1R2P(OH)+2. The pK of this phosphonium entities is lying in the range -2, -4. These results were confirmed by 31P NMR titration. The occurrence of such a phosphonium ion in aqueous solutions might be of crucial importance for biochemical reactions and interactions, owing to the large spread of phosphoryl group in biomolecules and keeping in mind that intracellular compartments are more likely concentrated media with little free water than real aqueous solutions. Furthermore, pK's can be shifted by physical-chemical parameters like dielectric constant and electric field. This may involve at least fractional positive charge apparition that might be important in biochemical regulation by charge-charge and charge-dipole interactions. This finding will gain to be further explored on more complex molecules like phospholipids, nucleic acids and proteins.
- Azema,Ladame,Lapeyre,Zwick,Lakhdar-Ghazal
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- Effect of the molecular size of analytes on polydicetylene chromism
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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 conjurgated backbone.In addtion. the length of a alkyl spacer between the amine headgroup and the amide group of the diacetylene lipids is found to strongly affect thedegree 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, he development of a system that colori metrically 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.
- Seo, Donghwan,Kim, Jinsang
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- Kinetic and isotope effect studies on the intermediacy of ethyl metathiophosphate in ethanolysis of O-ethyl N-1-adamantyl phosphoramidothioate
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The fragmentation of O-ethyl N-l-adamantylphosphoramidothioate (1a) and its oxygen counterpart 1b was examined in ethanol at 65-100°C. The solvent hydrogen effect kEtOH/kEtOD and kinetic nitrogen effect k14/k15 were determined at 80°C. The rates and parameters of activation of ethanolysis of 1a and 1b are slightly different. The solvent effect kEtOH/kEtOD was found to be equal to 0.84 ± 0.05 for 1a and 0.83 ± 0.04 for 1b. The nitrogen effect k14/k15 was found to be sensitive to replacement of sulfur by oxygen, and equal to 1.0083 ± 0.0004 for 1a and 1.0065 ± 0.0006 for 1b. The data indicate that proton transfer from the OH group to the amine moiety precedes the P-N bond breakage. The kinetic nitrogen isotope effect for the amine elimination recalculated for the pre-equilibrium step is equal to 1.0232 for 1a and 1.0215 for 1b. These results are consistent with the intermediacy of ethyl metathiophosphate in the solvolysis of 1a.
- Jankowski, Stefan,Quin, Louis D.,Paneth, Piotr,O'Leary, Marion H.
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- MIL-101(Cr) with incorporated polypyridine zinc complexes for efficient degradation of a nerve agent simulant: spatial isolation of active sites promoting catalysis
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Development of an efficient catalyst for degradation of organophosphorus toxicants is highly desirable. Herein, an MIL-101(Cr)LZn catalyst was fabricated by incorporating polypyridine zinc complexes into a MOF to achieve the spatial isolation of active si
- Zhang, Kai,Cao, Xingyun,Zhang, Zhiyan,Cheng, Yong,Zhou, Ying-Hua
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supporting information
p. 1995 - 2000
(2021/02/26)
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- Paraoxonase Mimic by a Nanoreactor Aggregate Containing Benzimidazolium Calix and l-Histidine: Demonstration of the Acetylcholine Esterase Activity
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An anion-mediated preorganization approach was used to design and synthesize the benzimidazolium-based calix compound R1?2 ClO4?. X-ray crystallography analysis revealed that the hydrogen-bonding interactions between the benzimidazol
- Singh, Amanpreet,Saini, Sanjeev,Mayank,Kaur, Navneet,Singh, Ajnesh,Singh, Narinder,Jang, Doo Ok
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p. 5737 - 5744
(2021/03/08)
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- METHOD FOR PRODUCING PHOSPHOESTER COMPOUND
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PROBLEM TO BE SOLVED: To provide a method whereby, a phosphate compound selected from the group consisting of orthophosphoric acid, phosphonic acid, phosphinic acid, and anhydrides of them is used as raw material and, by one stage reaction, a corresponding phosphoester compound is produced. SOLUTION: To an aqueous solution of a phosphate compound, added is an organic silane or siloxane compound having an alkoxy group or an aryloxy group, and the mixture is subjected to a heating reaction, thereby producing a corresponding phosphoester compound without requiring a catalyst. SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT
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Paragraph 0023-0025
(2021/09/27)
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- Organic-inorganic hybrid thorium polyacid salt and preparation method and application thereof
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The invention discloses an organic-inorganic hybrid thorium polyacid salt of which the chemical formula is {Th (DMSO) 6 (H2O) [SiW12O40]}. 2H2O, wherein DMSO is dimethyl sulfoxide, the molecular formula of thorium polyacid salt is C12H42O49S6SiThW12, the molecular weight of thorium polyacid salt is 3629, the thorium polyacid salt is a monoclinic system, the space group is P21/c, and the cell parameters of thorium polyacid salt are as follows: alpha = 90 degrees, beta = 99.4970 (10) degrees, gamma = 90 degrees and Z = 4. The thorium polyacid salt synthesized by the method has the characteristics of simplicity in synthesis, convenience in operation, high catalyst yield, mild reaction conditions, quickness in degradation, high degradation rate and the like and can be recycled without secondary pollution.
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Paragraph 0027, 0028
(2020/07/21)
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- Microwave-assisted nucleophilic degradation of organophosphorus pesticides in propylene carbonate
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Propylene carbonate is becoming a suitable green alternative to volatile organic solvents in the study of chemical reactions. In this study, an efficient method for nucleophilic degradation of five organophosphorus pesticides, fenitrothion, malathion, diazinon, parathion, and paraoxon, using propylene carbonate as a solvent is proposed. The effect of changing the nature of the nucleophile and the influence of microwave (MW) heating were investigated. A screening of temperatures (50 °C-120 °C) was performed under microwave heating. The pesticide degradation was followed by 31P NMR, and the extent of conversion (%) was calculated by the integration of phosphorus signals. Keeping in mind that recently it has been reported that some ionic liquids play a nucleophilic role, in this work we report for the first time the degradation of organophosphorus pesticides by using an amino acid-based ionic liquid such as Bmim[Ala] as a nucleophile and a bio-based solvent (propylene carbonate) as a reaction medium in combination with microwave heating. This journal is
- Millán, Daniela,Pavez, Paulina,Rojas, Mabel,Tapia, Ricardo A.
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supporting information
p. 7868 - 7875
(2020/11/02)
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- METHOD FOR PRODUCING PHOSPHONIC ACID DERIVATIVE
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PROBLEM TO BE SOLVED: To provide a method for producing a phosphonic acid derivative, in which the reaction proceeds under relatively mild reaction conditions without using hydrogen halide or a metal catalyst. SOLUTION: Provided is a method for producing a phosphonic acid derivative represented by formula (1), comprising a step in which an ester group-containing phosphonic acid derivative is reacted in a solvent or without a solvent in the presence of a superacid catalyst. (In formula (1), R1 and R2 are each independently a substituted or unsubstituted hydrocarbon group that may contain a heteroatom, n is a natural number of 1 to 3, m is a natural number of 0 to 2, o is a natural number of 0 to 1, and n + m + o = 3.). SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT
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Paragraph 0053; 0055
(2020/10/27)
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- Wet and dry processes for the selective transformation of phosphonates to phosphonic acids catalyzed by br?nsted acids
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A "wet"process and two "dry"processes for converting phosphonate esters to phosphonic acids catalyzed by a Bronsted acid have been developed. Thus, in the presence of water, a range of alkyl-, alkenyl-, and aryl-substituted phosphonates can be generally hydrolyzed to the corresponding phosphonic acids in good yields catalyzed by trifluoromethyl sulfonic acid (TfOH) at 140 °C (the wet process). On the other hand, with specific substituents of the phosphonate esters, the conversion to the corresponding phosphonic acids can be achieved under milder conditions in the absence of water (the dry process). Thus, the conversion of dibenzyl phosphonates to the corresponding phosphonic acids took place smoothly at 80 °C in toluene or benzene in high yields. Moreover, selective conversion of benzyl phosphonates RP(O)(OR′)(OBn) to the corresponding mono phosphonic acids RP(O)(OR′)(OH) can also be achieved under the reaction conditions. The dealkylation via the generation of isobutene of ditert- butyl phosphonate, and the related catalysis by TfOH took place even at room temperature to give the corresponding phosphonic acids in good to high yields. Nafion also shows high catalytic activity for these reactions. By using Nafion as the catalyst, phosphonic acids could be easily prepared on a large scale via a simple process.
- Li, Chunya,Saga, Yuta,Onozawa, Shun-Ya,Kobayashi, Shu,Sato, Kazuhiko,Fukaya, Norihisa,Han, Li-Biao
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p. 14411 - 14419
(2020/12/29)
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- Reactivity and mechanism of α-nucleophile scaffolds as catalytic organophosphate scavengers
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Despite their unique benefits imparted by their structure and reactivity, certain α-nucleophile molecules remain underexplored as chemical inactivators for the topical decontamination of reactive organophosphates (OPs). Here, we present a library of thirty α-nucleophile scaffolds, each designed with either a pyridinium aldoxime (PAM) or hydroxamic acid (HA) α-nucleophile core tethered to a polar or charged scaffold for optimized physicochemical properties and reactivity. These library compounds were screened for their abilities to catalyze the hydrolysis of a model OP, paraoxon (POX), in kinetic assays. These screening experiments led to the identification of multiple lead compounds with the ability to inactivate POX two- to four-times more rapidly than Dekon 139 - the active ingredient currently used for skin decontamination of OPs. Our mechanistic studies, performed under variable pH and temperature conditions suggested that the differences in the reactivity and activation energy of these compounds are fundamentally attributable to the core nucleophilicity and pKa. Following their screening and mechanistic studies, select lead compounds were further evaluated and demonstrated greater efficacy than Dekon 139 in the topical decontamination of POX in an ex vivo porcine skin model. In addition to OP reactivity, several compounds in the PAM class displayed a dual mode of activity, as they retained the ability to reactivate POX-inhibited acetylcholine esterase (AChE). In summary, this report describes a rationale for the hydrophilic scaffold design of α-nucleophiles, and it offers advanced insights into their chemical reactivity, mechanism, and practical utility as OP decontaminants.
- Wong, Pamela T.,Bhattacharjee, Somnath,Cannon, Jayme,Tang, Shengzhuang,Yang, Kelly,Bowden, Sierra,Varnau, Victoria,O'Konek, Jessica J.,Choi, Seok Ki
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supporting information
p. 3951 - 3963
(2019/04/30)
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- Versatile catalysts constructed from hybrid polyoxomolybdates for simultaneously detoxifying sulfur mustard and organophosphate simulants
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Chemical warfare agents (CWAs) containing sulfur mustard and organophosphates are among the most toxic materials known to mankind and have caused lots of casualties during wars and terrorist attacks. Development of catalysts with selective oxidation and hydrolysis abilities for detoxification of these two types of CWAs is highly desired. Here, we report a series of carboxylic acid modified polyoxomolybdate derivatives with high catalytic performance in the degradation two typical chemical warfare agent simulants: 2-chloroethyl ethyl sulfide (CEES) and diethyl cyanophosphonate (DECP), at room temperature. Our results demonstrate that CEES can be highly-selectively degraded to the corresponding far less toxic 2-chloroethyl ethyl sulfoxide (CEESO) with the oxidant H2O2 within 12 minutes, and DECP is almost completely hydrolysed to nontoxic products within 10 minutes. The catalytic activities of these compounds were found to be influenced by the metal cations, carboxylic acid ligands and heteroatoms of polyoxoanions. The corresponding order is respectively Co2+ > Ni2+, Zn2+, Mn2+; PABA > Ala, Ac; AsMo > TeMo.
- Hou, Yujiao,An, Haiyan,Chang, Shenzhen,Zhang, Jie
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p. 2445 - 2455
(2019/06/13)
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- Regiodivergent Ring-Opening Cross-Coupling of Vinyl Aziridines with Phosphorus Nucleophiles: Access to Phosphorus-Containing Amino Acid Derivatives
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Catalytic ring-opening phosphonation and phosphatation of vinyl aziridines have been developed in a regiodivergent fashion, giving linear and branched products. Generation of P-centered radicals enables SN2′-type ring-opening reactions of vinyl aziridines to afford δ-amino alkylphosphorus products at room temperature. On the other hand, in situ generated phosphate anions via the Ag-catalyzed aerobic oxidation of phosphonyl reactants underwent SN2 reaction to provide branched phosphorus-containing amine products. Furthermore, this divergent methodology serves as a powerful tool for the stereospecific synthesis of phosphorus-containing amino acid derivatives.
- Kang, Dahye,Kim, Taehwan,Lee, Hyunpyo,Hong, Sungwoo
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supporting information
p. 7571 - 7575
(2018/11/23)
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- Dual function of amino acid ionic liquids (Bmim[AA]) on the degradation of the organophosphorus pesticide, Paraoxon
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The synthesis of a series of ionic liquids using 1-butyl 3-methylimidazolium (Bmim+) as a cation and different amino acids (AA) as anions (Bmim[AA]) is described. These ILs were used for the first time as reaction media to achieve more eco-friendly Paraoxon degradation. The results show that the degradation of Paraoxon in these Bmim[AA]s is accomplished with great efficiency and without an extra nucleophilic agent. Therefore, we propose that all the Bmim[AA]s used in this study have a dual role in the outcome of this reaction; as a nucleophile and a solvent to carry out degradation of the organophosphorous pesticide, Paraoxon. Both kinetics and product distribution results found in this study for Paraoxon degradation turned out to be promising, because this process is achieved in a reaction medium with a better environmental profile.
- Morales, Javiera I.,Figueroa, Roberto,Rojas, Mabel,Millán, Daniela,Tapia, Ricardo A.,Pavez, Paulina
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p. 7446 - 7453
(2018/10/24)
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- An Unusual Two-Step Hydrolysis of Nerve Agents by a Nanozyme
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Organophosphate-based nerve agents irreversibly inhibit acetylcholinesterase enzyme, leading to respiratory failure, paralysis and death. Several organophosphorus hydrolases are capable of degrading nerve agents including pesticides and insecticides. Development of stable artificial enzymes capable of hydrolysing nerve agents is important for the degradation of environmentally toxic organophosphates. Herein, we describe a Zr-incorporated CeO2 nanocatalyst that can be used for an efficient capture and hydrolysis of nerve agents such as methyl paraoxon to less toxic monoesters. This unusual sequential degradation pathway involves a covalently linked nanocatalyst-phosphodiester intermediate.
- Khulbe, Kritika,Roy, Punarbasu,Radhakrishnan, Anusree,Mugesh, Govindasamy
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p. 4840 - 4845
(2018/09/27)
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- Direct, oxidative halogenation of diaryl- or dialkylphosphine oxides with (dihaloiodo)arenes
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The oxidative halogenation of diaryl- or dialkylphosphine oxides with the hypervalent iodine reagents (difluoroiodo)toluene (p-TolIF2, 1) and (dichloroiodo)benzene (PhICl2, 2) is reported. Phosphoric fluorides could be recovered in 32–75% yield, or they could be trapped with EtOH to give the corresponding phosphinate in typically good yield. Phosphoric chlorides were not readily isolable, and were trapped with alcohol and amine nucleophiles, giving diaryl- or dialkylphos-phinates and phosphinamides in up to 90% yield.
- Eljo, Jasmin,Murphy, Graham K.
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supporting information
p. 2965 - 2969
(2018/06/30)
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- Rapid Destruction of Two Types of Chemical Warfare Agent Simulants by Hybrid Polyoxomolybdates Modified by Carboxylic Acid Ligands
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Four chain-like hybrid compounds based on mixed carboxylic acid ligands-modified polyoxomolybdates, K2H[(H2O)4M][AsMo6O21(Ala)(PHBA)2]·nH2O 1-4 (M = Co, Ni, Zn, Mn; Ala = alanine; PHBA = p-hydroxybenzonic acid), were prepared and characterized by elemental analysis, IR spectroscopy, solid diffuse reflective spectroscopy, TG analysis, powder X-ray diffraction, and single-crystal X-ray diffraction. Four isostructural compounds 1-4 not only represent the extended architectures constructed from two different organic ligands-modified polyoxometalates but also can rapidly catalyze the degradation of two chemical warfare agent simulants, 2-chloroethyl ethyl sulfide (CEES) and diethyl cyanophosphonate (DECP), at room temperature. The catalytic results were analyzed and confirmed by GC-FID, GC-MS, and 1HNMR techniques. Within 5 min, CEES was high-selectively oxidized to the corresponding nontoxic 2-chloroethyl ethyl sulfoxide (CEESO) using heterogeneous catalyst 1 with the oxidant H2O2 (conversion % = 98.5%, selectivity % > 99.9%). FTIR, PXRD techniques, and the following cycles also ascertained the stability and structural integrity of 1 in the oxidation reaction. Within 10 min, DECP can be almost entirely hydrolyzed to the nontoxic products catalyzed by 1 (conversion % = 99.0%). To our knowledge, they are in the rank of highly active catalysts for the degradation of CEES and DECP to date, accompanied by the advantages of steady reuse.
- Hou, Yujiao,An, Haiyan,Zhang, Yumeng,Hu, Tao,Yang, Wei,Chang, Shenzhen
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p. 6062 - 6069
(2018/07/24)
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- A Versatile Self-Detoxifying Material Based on Immobilized Polyoxoniobate for Decontamination of Chemical Warfare Agent Simulants
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A decontaminating composite, Mg3Al-LDH-Nb6, has been successfully prepared by immobilizing Lindqvist [H3Nb6O19]5? (Nb6) into a Mg3Al-based layered double hydroxide (Mg3Al-LDH). To our knowledge, this represents the first successful approach to the immobilization of polyoxoniobate. As a versatile catalyst, Mg3Al-LDH-Nb6 can effectively catalyze the degradation of both vesicant and nerve agent simulants by multiple pathways under mild conditions. Specifically, the sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES), is converted into the corresponding nontoxic 2-chloroethyl ethyl sulfoxide (CEESO) by selective oxidation, whereas the Tabun (G-type nerve agent) simulant, diethyl cyanophosphonate (DECP), and the VX (V-type nerve agent) simulant, O,S-diethyl methylphosphonothioate (OSDEMP), are detoxified through hydrolysis and perhydrolysis, respectively. A possible mechanism is proposed on the basis of control experiments and spectroscopic studies. The Mg3Al-LDH-Nb6 composite exhibits remarkable robustness and can be readily reused for up to ten cycles with negligible loss of its catalytic activity. More importantly, a protective “self-detoxifying” material has easily been constructed by integrating Mg3Al-LDH-Nb6 into textiles. In this way, the flexible and permeable properties of textiles have been combined with the catalytic activity of polyoxoniobate to remove 94 % of CEES in 1 h by using nearly stoichiometric dilute H2O2 (3 %) as oxidant with 96 % selectivity.
- Dong, Jing,Lv, Hongjin,Sun, Xiangrong,Wang, Yin,Ni, Yuanman,Zou, Bo,Zhang, Nan,Yin, Anxiang,Chi, Yingnan,Hu, Changwen
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p. 19208 - 19215
(2019/01/03)
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- Degradation of Paraoxon and the Chemical Warfare Agents VX, Tabun, and Soman by the Metal-Organic Frameworks UiO-66-NH2, MOF-808, NU-1000, and PCN-777
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In recent years, Zr-based metal-organic frameworks (MOFs) have been developed that facilitate catalytic degradation of toxic organophosphate agents, such as chemical warfare agents (CWAs). Because of strict regulations, experiments using live agents are not possible for most laboratories and, as a result, simulants are used in the majority of cases. Reports that employ real CWAs are scarce and do not cover the whole spectrum of agents. We here present a comparative study in which UiO-66-NH2, NU-1000, MOF-808, and PCN-777 are evaluated for their effectiveness in the degradation of paraoxon and the chemical warfare agents tabun, VX, and soman, in N-ethylmorpholine buffer (pH 10) as well as in pure water. All MOFs showed excellent ability to degrade the agents under basic conditions. It was further disclosed that tabun is degraded by different mechanisms depending on the conditions. The presence of an amine, either as part of the MOF structure (UiO-66-NH2) or in the agent itself (VX, tabun), is the most important factor governing degradation rates in water. The results show that MOFs have great potential in future protective applications. Although the use of simulants provides valuable information for initial screening and selection of new MOFs, the use of live agents revealed additional mechanisms that should aid the future development of even better catalysts.
- De Koning, Martijn C.,Van Grol, Marco,Breijaert, Troy
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supporting information
p. 11804 - 11809
(2017/10/10)
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- A Polyoxoniobate–Polyoxovanadate Double-Anion Catalyst for Simultaneous Oxidative and Hydrolytic Decontamination of Chemical Warfare Agent Simulants
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A novel double-anion complex, H13[(CH3)4N]12[PNb12O40(VVO)2?(VIV4O12)2]?22 H2O (1), based on bicapped polyoxoniobate and tetranuclear polyoxovanadate was synthesized, characterized by routine techniques and used in the catalytic decontamination of chemical warfare agents. Under mild conditions, 1 catalyzes both hydrolysis of the nerve agent simulant, diethyl cyanophosphonate (DECP) and selective oxidation of the sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES). In the oxidative decontamination system 100 % CEES was transformed selectively to nontoxic 2-chloroethyl ethyl sulfoxide and vinyl ethyl sulfoxide using nearly stoichiometric 3 % aqueous H2O2 with a turnover frequency (TOF) of 16 000 h?1. Importantly, the catalytic activity is maintained even after ten recycles and CEES is completely decontaminated in 3 mins without formation of the highly toxic sulfone by-product. A three-step oxidative mechanism is proposed.
- Dong, Jing,Hu, Jufang,Chi, Yingnan,Lin, Zhengguo,Zou, Bo,Yang, Song,Hill, Craig L.,Hu, Changwen
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supporting information
p. 4473 - 4477
(2017/04/11)
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- Polyoxometalate-based gelating networks for entrapment and catalytic decontamination
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We report the synthesis and characterization of a new class of organic/inorganic hybrid polymers composed of covalently-bound 1,3,5-benzenetricarboxamide linkers and anionic polyoxovanadate clusters with varying counter-cations. These materials form gels within seconds upon contact with polar aprotic organic liquids and catalyze the degradation of odorants and toxic molecules under mild conditions including aerobic oxidation of thiols, hydrogen peroxide-catalyzed oxidation of sulfides, and hydrolysis of organophosphate chemical warfare agent analogues.
- Sullivan, Kevin P.,Neiwert, Wade A.,Zeng, Huadong,Mehta, Anil K.,Yin, Qiushi,Hillesheim, Daniel A.,Vivek, Skanda,Yin, Panchao,Collins-Wildman, Daniel L.,Weeks, Eric R.,Liu, Tianbo,Hill, Craig L.
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supporting information
p. 11480 - 11483
(2017/10/23)
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- A visually detectable pH responsive zirconium metal-organic framework
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A halochromic Zr6-based metal-organic framework is synthesized using solvent-assisted linker incorporation (SALI) with NU-1000 as a platform and carboxylnaphthofluorescein as a pH sensitive ligand. The functionalized MOF can catalytically detoxify nerve agent simulants in addition to visually detecting the acidic byproduct produced during detoxification.
- Moon, Su-Young,Howarth, Ashlee J.,Wang, Timothy,Vermeulen, Nicolaas A.,Hupp, Joseph T.,Farha, Omar K.
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supporting information
p. 3438 - 3441
(2016/02/27)
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- Reactivity and selectivity of the reaction of: O, O -diethyl 2,4-dinitrophenyl phosphate and thionophosphate with thiols of low molecular weight
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A reactivity and selectivity study of O,O-diethyl 2,4-dinitrophenyl phosphate (1) and O,O-diethyl 2,4-dinitrophenyl thionophosphate (2) with a series of thiols of low molecular weight: N-acetyl cysteine (NAC), l-cysteine (Cys), homocysteine (Hcys), glutathione (GSH), and d-penicillamine (Pen) was conducted. Results show that (i) these nucleophiles only attack at the aromatic moiety of both triester derivatives, (ii) a kinetic control product by sulfhydryl attack of thiols was observed in the reactions of both triesters with Cys and Hcys, followed by an intramolecular amine attack leading to a thermodynamic control product. The kinetic study leads to the proposal of Meisenheimer complex formation and then proton transfer to the reaction media as the mechanism of these reactions.
- Santos,Aliaga,Alarcón,Torres,Céspedes,Pavez
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supporting information
p. 6479 - 6486
(2016/07/16)
-
- I2O5/DBU mediated direct α-phosphoryloxylation of ketones with H-phosphonates leading to α-hydroxyketone phosphates
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A simple and convenient procedure has been developed for the construction of α-hydroxyketone phosphates via I2O5/DBU mediated direct α-phosphoryloxylation of ketones with H-phosphonates. This new reaction proceeds through three steps involving α-iodination of ketones, oxidation of H-phosphonates, and nucleophilic substitution of α-iodo ketones to access a series of α-hydroxyketone phosphates of biological importance.
- Liu, Chunli,Wei, Wei,Yang, Daoshan,Zheng, Yuanyuan,Bi, Yanshuai,Chen, Min,Wang, Hua
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p. 6901 - 6906
(2015/08/24)
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- MULTIFUNCTIONAL SMALL MOLECULES
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The present invention relates to novel therapeutic dendrimer conjugates configured for the treatment and/or prevention of organophosphate poisoning. In particular, the present invention is directed to dendrimers complexed with organophosphate poisoning an
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Paragraph 0236
(2015/09/22)
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- Detection and remediation of organophosphorus compounds by oximate containing organogels
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A series of supramolecular diamide organogels containing a reactive compound for the remediation of organophosphorus (OP) species, in particular OP chemical warfare agents (CWAs), has been prepared in DMSO. The organogels have been found to absorb, encapsulate and decontaminate various OP CWA simulants in situ. At high simulant concentrations the gels also undergo a gel-sol transition releasing high local concentrations of remediation agent.
- Hiscock, Jennifer R.,Sambrook, Mark R.,Wells, Neil J.,Gale, Philip A.
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p. 5680 - 5684
(2015/09/28)
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- Kinetics and speciation of paraoxon hydrolysis by zinc(II)-azamacrocyclic catalysts
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Four Zn2+-azamacrocyclic complexes were investigated for their ability to catalyze the hydrolysis of the toxic organophosphate (OP) pesticide diethyl paraoxon. Of the four complexes studied, Zn2+-1,5,9-triazacyclododecane (Zn2+-[12]aneN3) was found to be the most effective catalyst with a pseudo-first order reaction rate of k = 6.08 ± 0.23 × 10-4 min-1. Using 31P nuclear magnetic resonance (NMR) spectroscopy, the two products diethyl phosphate (DEP) and ethyl (4-nitrophenyl) phosphate (E4NPP) were identified for both catalyzed and background hydrolysis of paraoxon. Reaction rate and selectivity for formation of the non-toxic DEP were observed to correlate with catalyst pKa. The rate of formation of toxic E4NPP, however, was independent of both the presence and nature of the catalyst. The potential roles of buffer concentration and product inhibition were also investigated. Background hydrolysis at elevated reaction temperatures (50°C) displayed no preference for DEP over that of E4NPP despite substantial differences between the characteristics (i.e., pKa values) of the two leaving groups (ethoxide vs. 4-nitrophenoxide anions). As with previous observations of these types of metal-catalyzed hydrolyses, we invoke the formation of a trigonal bipyramidal-like transition state involving a Zn-coordinated phosphate bond, with the leaving group at the apical position and the incoming HO- anion approaching from the opposite end. Kinetic rates for catalytic hydrolysis display an overwhelming propensity for DEP formation, and suggest the importance of steric restrictions on transition state structure, namely a concerted arrangement of the azamacrocycle in opposition to the bulky 4-nitrophenoxy group.
- Kennedy, Daniel J.,Mayer, Brian P.,Baker, Sarah E.,Valdez, Carlos A.
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supporting information
p. 123 - 131
(2015/08/24)
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- An ionically tagged water-soluble artificial enzyme promotes the dephosphorylation reaction with nitroimidazole: Enhanced ionic liquid effect and mechanism
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In this paper, we describe a novel synthesized ionically tagged water-soluble artificial enzyme (PI) that can efficiently cleave phosphate esters, with enhanced an ionic liquid effect through cooperative effects for the substrate activation and further nucleophilic reaction. The dephosphorylation reaction with PI was evaluated in the presence and absence of 2-methyl-4(5)-nitroimidazole, showing impressive rate enhancements of up to 2 × 106-fold, ascribed to the imidazolide species known as excellent nucleophiles, and formed favorably at lower pH values in the presence of PI.
- Ferreira, José G. L.,Ramos, Luciana M.,De Oliveira, Aline L.,Orth, Elisa S.,Neto, Brenno A. D.
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p. 5979 - 5983
(2015/06/16)
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- Photorelease of phosphates: Mild methods for protecting phosphate derivatives
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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 excited state, are robust under ambient conditions and can be carried on to 100% conversion. Similar results were found with diethyl 2-(4-methoxy-1-naphthyl)-2-oxoethyl phosphate (14b), although it was significantly less efficient compared with 14a. A key step in the deprotection reaction in aq MeOH is considered to be a Favorskii rearrangement of the naphthyl ketone motif of 14a,b to naphthylacetate esters 25 and 26. Disruption of the ketone-naphthyl ring conjugation significantly shifts the photoproduct absorption away from the effective incident wavelength for decaging of 14, driving the reaction to completion. The Favorskii rearrangement does not occur in aqueous acetonitrile although diethyl phosphate is released. Other substitution patterns on the naphthyl or quinolin-5-yl core, such as the 2,6-naphthyl 10 or 8-benzyloxyquinolin-5-yl 24 platforms, also do not rearrange by aryl migration upon photolysis and, therefore, do not proceed to completion. The 2,6-naphthyl ketone platform instead remains intact whereas the quinolin-5-yl ketone fragments to a much more complex, highly absorbing reaction mixture that competes for the incident light.
- Senadheera, Sanjeewa N.,Yousef, Abraham L.,Givens, Richard S.
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p. 2038 - 2054
(2014/11/07)
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- Neutral 1,3-diindolylureas for nerve agent remediation
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Efficient neutralization of nerve-agent simulants by 1,3-diindolylureas in a neutral medium was investigated (see scheme; DCP=diethylchlorophosphate, DCNP=diethylcyanophosphonate). The rate of hydrolysis of the simulants was found to increase by as much as 45 % in the presence of these compounds. A mechanism based on the simulant complexation was established. Copyright
- Barba-Bon, Andrea,Costero, Ana M.,Parra, Margarita,Gil, Salvador,Martínez-Má?ez, Ram?n,Sancen?n, Félix,Gale, Philip A.,Hiscock, Jennifer R.
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p. 1586 - 1590
(2013/02/25)
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- Mechanisms of degradation of paraoxon in different ionic liquids
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Herein, the reactivity and selectivity of the reaction of O,O-diethyl 4-nitrophenyl phosphate triester (Paraxon, 1) with piperidine in ionic liquids (ILs), three conventional organic solvents (COS), and water is studied by 31P NMR, UV-vis, and GC/MS. Three phosphorylated products are identified as follows: O,O-diethyl piperidinophosphate diester (2), O,O-diethyl phosphate (3), and O-ethyl 4-nitrophenyl phosphate diester (4). Compound 4 also reacts with piperidine to yield O-ethyl piperidinophosphate monoester (5). The results show that both the rate and products distribution of this reaction depend on peculiar features of ILs as reaction media and the polarity of COS.
- Pavez, Paulina,Millan, Daniela,Morales, Javiera I.,Castro, Enrique A.,Lopez A., Claudio,Santos, Jose G.
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p. 9670 - 9676
(2013/10/22)
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- Molecular engineering of organophosphate hydrolysis activity from a weak promiscuous lactonase template
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Rapid evolution of enzymes provides unique molecular insights into the remarkable adaptability of proteins and helps to elucidate the relationship between amino acid sequence, structure, and function. We interrogated the evolution of the phosphotriesteras
- Meier, Monika M.,Rajendran, Chitra,Malisi, Christoph,Fox, Nicholas G.,Xu, Chengfu,Schlee, Sandra,Barondeau, David P.,Hoecker, Birte,Sterner, Reinhard,Raushel, Frank M.
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supporting information
p. 11670 - 11677
(2013/09/02)
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- Fluorescein analogues as photoremovable protecting groups absorbing at ~520 nm
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A new photoremovable protecting group, (6-hydroxy-3-oxo-3H-xanthen-9-yl) methyl (1), with a molar absorption coefficient ε of ~4 × 10 4 m-1 cm-1 at ~520 nm for the release of carboxylates or phosphates is reported. Three derivatives of 1 (diethyl phosphate, acetate, and bromide) were isolated as complexes with DDQ and shown to release the ligands with quantum yields ≤2.4% in aqueous solution.
- ?ebej, Peter,Wintner, Jürgen,Müller, Pavel,Slanina, Tomá?,Al Anshori, Jamaludin,Antony, Lovely Angel Panamparambil,Klán, Petr,Wirz, Jakob
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p. 1833 - 1843
(2013/04/10)
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- Dual nucleophilic substitution reactions of O,O-diethyl 2,4-dinitrophenyl phosphate and thionophosphate triesters
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The reactions of the title compounds with phenoxides, secondary alicyclic (SA) amines, and pyridines, in 44 wt% ethanol-water, at 25°C and an ionic strength of 0.2 M, were subjected to kinetic and product studies. From analytical techniques (HPLC and NMR), two pathways were detected (nucleophilic attack at the phosphoryl center and at the C-1 aromatic carbon) for the reactions of all the nucleophiles with the phosphate (2) and for the pyridinolysis of the thionophosphate (1). Only aromatic nucleophilic substitution was found for the reactions of 1 with phenoxides and SA amines. For the dual reactions, the nucleophilic rate constants (kN) were separated in two terms: documentclass{article}usepackage{amssymb} pagestyle{empty}begin{document}k-{rm N}^{rm P}end{document} and documentclass{article}usepackage{amssymb}pagestyle{empty}begin{document}k-{ rm N}^{{rm Ar}}end{document}, which are the rate constants for the corresponding electrophilic centers. The absence of a break in the Bronsted-type plots for the attack at P is consistent with concerted mechanisms. The Bronsted slopes, βAr 0.32-0.71, for the attack at the aromatic C-1, are in agreement with stepwise mechanisms where formation of a Meisenheimer complex is the rate-determining step. 2013 Wiley Periodicals, Inc. Int J Chem Kinet 45: 202-211, 2013 Copyright
- Aguayo, Raul,Arias, Felipe,Canete, Alvaro,Zuniga, Carolina,Castro, Enrique A.,Pavez, Paulina,Santos, Jose G.
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supporting information
p. 202 - 211
(2013/03/14)
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- Reactivity of an electrophilic hypervalent iodine trifluoromethylation reagent with hydrogen phosphates - A mechanistic study
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The electrophilic trifluoromethylation of hydrogen phosphates with the reagent trifluoromethyl-1,3-dihydro-3,3-dimethyl-1,2-benziodoxole (1) was studied by means of initial rates determined for pseudo first order setups and subsequent Taft analysis of the calculated relative rates. A positive polar sensitivity factor, indicative of a negative charge forming during the rate-determining step, was found for the whole data set.
- Santschi, Nico,Geissbühler, Patrik,Togni, Antonio
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experimental part
p. 83 - 86
(2012/03/27)
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- Kinetics of degradation of sulfur mustard and sarin simulants on HKUST-1 metal organic framework
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The applicability of HKUST-1 for the degradation of sulfur mustard and sarin simulants was studied with and without coadsorbed water. Degradation was found to be via hydrolysis and dependent on the nucleophilic substitution reaction, vapour pressure and molecular diameter of the toxicants.
- Roy, Anuradha,Srivastava, Avanish K.,Singh, Beer,Shah, Dilip,Mahato, Timir Haran,Srivastava, Anchal
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supporting information
p. 12346 - 12348
(2012/11/07)
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- Novel photolabile protecting group for phosphate compounds
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A novel photolabile protecting group, thiochromone S,S-dioxide, containing the diazomethyl group for protection of phosphate derivatives is described. Deprotection of the successfully protected phosphate derivatives proceeded smoothly under photoirradiation using an ultrahigh-pressure mercury lamp to recover the corresponding phosphates quantitatively, and the photoproduct derived from the thiochromone derivative showed high fluorescence intensity. Georg Thieme Verlag Stuttgart · New York.
- Zhang, Youlai,Tanimoto, Hiroki,Nishiyama, Yasuhiro,Morimoto, Tsumoru,Kakiuchi, Kiyomi
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scheme or table
p. 367 - 370
(2012/03/11)
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- Simple methanesulfonates are hydrolyzed by the sulfatase carbonic anhydrase activity
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The possible sulfatase activity of several carbonic anhydrase (CA, EC 4.2.1.1) isoforms have been investigated with a series of synthesized methanesulfonate derivatives of phenols. Four α-CA isozymes, i.e. hCA I, hCA II, hCA IV and hCA VI (h=human isoform), were included in the study. We evidenced that the original sulfonate esters are being hydrolyzed effectively to the corresponding phenols which there after act as CA inhibitors. The KI-s of these compounds ranged from 10.24 to 4012 μM against hCA I, 0.10 to 35.42 μM against hCA II, 0.49 to 45.06 μM against hCA IV and 3.27 to 608 μM against CA VI, respectively. The relevant sulfatase activity of CA with these esters is amazing considering the fact that 4-nitrophenyl-sulfate, an activated ester, is not a substrate of these enzymes.
- Kazancio?lu, Elif Akin,Güney, Murat,?entürk, Murat,Supuran, Claudiu T.
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p. 880 - 885
(2013/02/23)
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- GELLED HYDROCARBONS FOR OILFIELD PROCESSES, PHOSPHATE ESTER COMPOUNDS USEFUL IN GELLATION OF HYDROCARBONS AND METHODS FOR PRODUCTION AND USE THEREOF
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Phosphate esters useful for gelling hydrocarbons in combination with a metal source are disclosed along with methods of preparation of the phosphate esters. Fouling in oil refinery towers has been attributed due to distillation of impurities present in phosphate esters used to gel hydrocarbons for oil well fracturing. The improved method of preparation of the phosphate ester results in a product that substantially reduces or eliminates volatile phosphorus, which is phosphorus impurities that distill up to 250° C., and increases the high temperature viscosity of the hydrocarbon gels formed using the phosphate esters.
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Page/Page column 6
(2011/04/14)
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- Distribution and elimination of 14C-ethion insecticide in chamomile flowers and oil
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The residual fate of 14C-ethion labeled at the ethyl group in chamomile flowers and oil was studied. 14C-ethion and some of its degradation products have been prepared for the present investigation. 14C-residues in its flowers and oil were determined at different time intervals. Chromatographic analysis of chamomile oil extracts revealed the presence of the parent compound together with four metabolites, which were identified as ethion monooxon, ethion dioxon, O,O-diethyl phosphorothioate, and O-ethyl phosphorothioate. Effect of drying on ethion residues in chamomile flowers was investigated. Ethion residues were decreased by sun drying of chamomile flowers. The percentage of removal was 18%-47%. Effect of using low cost adsorbents for removal of ethion residues from chamomile oil was investigated. The removal percentage due to adsorption was 100% for CaO and saw dust adsorbers and for watermelon peels, bagass, and rice bran adsorbers were 36%, 41%, and 90%, respectively. Our results proved that the addition of CaO saw dust and rice bran reduced the pesticide residues, so we recommend the addition of these adsorbents during the extraction process to reduce the risk of pesticide residues on chamomile oil. Copyright Taylor & Francis Group, LLC.
- Abdel-Gawad,Abdelhameed,Elmesalamy,Hegazi
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experimental part
p. 2122 - 2134
(2011/12/02)
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- Nucleophilic oxidizing systems based on hydrogen peroxide for decomposition of ecotoxicants
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The kinetics of oxidation of methylsulfanylbenzene and nucleophilic decomposition of diethyl 4-nitrophenyl phosphate with hydrogen peroxide in the presence of ammonium hydrogen carbonate or boric acid in aqueous, aqueous-alcoholic, micellar, and microemulsion media were studied. Quantitative parameters of the examined processes were determined, and the possibility of using hydrogen peroxide for the design of oxidative nucleophilic decontaminating systems was demonstrated.
- Vakhitova,Matvienko,Taran,Lakhtarenko,Popov
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scheme or table
p. 965 - 973
(2011/10/19)
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- NANO-REAGENTS WITH COOPERATIVE CATALYSIS AND THEIR USES IN MULTIPLE PHASE REACTIONS
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Nano-reagents with catalytic activity are provided herein. The nanocatalyst comprises at least one amino acid attached to a nanoparticle, wherein the reactive side chain of the amino acid catalyzes a chemical or biological reaction. Methods of using these nano-reagents to catalyze reactions in solution or in multiple phases are also provided, as are methods of making these nanocatalysts.
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Page/Page column 11-12; sheet 8/11
(2011/08/08)
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- Preparation of a PTE simulacrum based on surface molecular imprinting
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Firstly, we synthesized N-methacryloyl-histidine monomer and N-methacryloyl-histidine-Cu2+ complex (MAH-Cu2+). Then the molecular imprinting polymers (MIP) has been prepared by surface grafting on uniform polystyrene (PS) core using
- Guo, Yong,Yang, Ying,Guo, Tian Ying
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experimental part
p. 493 - 496
(2012/01/19)
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- L-Gel formulation and decontamination reaction of its active ingredient (oxone) against mustard and VX nerve agent simulants
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L-Gel is an effective decontamination reagent against chemical and biological warfare agents. To achieve optimized formulation of L-Gel, several formulations with different proportional amounts of oxone (oxidizer) and Cab-O-Sil (gelling agent) were prepared and their viscosities and densities were measured. Final optimized formulation of gel was obtained as a 0.25 M aqueous solution of oxone gelled with 13%W/W of Cab-O-Sil EH-5. The L-Gel active ingredient (oxone) was tested against O,O,S-triethyl phosphorothioate (TEPT) as VX simulant and methyl phenyl sulfide (MPS) and chloroethyl phenyl sulfide (CEPS) as HD simulants. Decontamination of TEPT by a 10-fold excess amount of oxone was completed within 7.5 min with a kinetic rate constant of 0.097 S -1. In the presence of oxone, MPS was converted to methyl phenyl sulfoxide and methyl phenyl sulfone with a higher reaction rate than CEPS, decontaminated product of which was chloroethyl phenyl sulfone. Copyright Taylor & Francis Group, LLC.
- Farahipour, Mahdi,Fakhraian, Hossein,Mirzaei, Akbar,Hosseini, Morteza Ali
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experimental part
p. 2303 - 2310
(2012/03/27)
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- A mesoporous, silica-immobilized-nanoparticle colorimetric chemosensor for the detection of nerve agents
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A new and an easy-to-make colorimetric azo-pyridine, 1, and its recyclable mesoporous silica-immobilized nanoparticles for nerve-agent detection are synthesized. The binding site, comprising an azo-pyridine moiety, is capable of selectively sensing diethylchlorophosphate (DCP), one of the nerve-agent mimics of chemical-warfare agents, over a series of other phosphate compounds. Compound 1 shows ratiometric changes in absorption spectroscopy to the extent of a 60 nm red-shift upon the addition of DCP, mainly due to a change in the intramolecular charge transfer (ICT) in 1 . The color change of receptor 1 from yellow to red in the concentration region = 1.0 × 10 -6 M is sufficient for the selective detection of the DCP nerve-agent mimic by the naked eye. With regards to solid-phase application, mesoporous silica nanoparticles using 1 ( MSIAP ) are also prepared using a sol-gel grafting reaction. The color of the MSIAP also changes from red to yellow when dipped into an aqueous DCP solution, and turns back to red when treated with NaOH solution, with nontoxic diethylphosphoric acid being given off. The absorption changes of MSIAP in the presence of DCP are consistent within the 3-9 pH range.
- Kim, Hyun Jung,Lee, Ji Ha,Lee, Hyejin,Lee, Jae Hong,Lee, Joung Hae,Jung, Jong Hwa,Kim, Jong Seung
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scheme or table
p. 4035 - 4040
(2012/03/22)
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- Cationic and radical intermediates in the acid photorelease from aryl sulfonates and phosphates
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The irradiation of a series of phenyl sulfonates and phosphates leads to the quantitative release of acidity with a reasonable quantum yield (≈0.2). Products characterization, ion chromatography analysis and potentiometric titration are consistent with the intervening of two different paths in this reaction, viz. cationic with phosphates and (mainly) radical with sulfonates. The Royal Society of Chemistry and Owner Societies 2011.
- Terpolilli, Marco,Merli, Daniele,Protti, Stefano,Dichiarante, Valentina,Fagnoni, Maurizio,Albini, Angelo
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experimental part
p. 123 - 127
(2012/01/03)
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- PHOTODISSOCIABLE PROTECTIVE GROUP
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The present invention provides a photolabile protecting group that can be removed by light irradiation under mild conditions. More specifically, the present invention provides a method comprising protecting a reactive functional group (e.g., a hydroxyl group, amino group, carboxyl group, carbonyl group, phosphodiester group, etc.) by the photolabile protecting group, and then removing the photolabile protecting group simply by light irradiation under neutral conditions. The present invention relates to a compound represented by Formula (3): wherein Ar1 is an optionally substituted aromatic or heteroaromatic ring, Ar2 is an optionally substituted aryl or heteroaryl group, X is a leaving group, and n is an integer of 1 or 2; and a method of protecting and deprotecting an amino group etc. using the compound.
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Page/Page column 40-41
(2011/02/25)
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- Development of reactive methacrylates based on glycidyl methacrylate
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Six methacrylate monomers have been synthesized for use as reactive diluents in dental composites and evaluated to investigate the relationship between molecular structure and monomer reactivity. Four were synthesized by reactions of glycidyl methacrylate (GMA) with various acids, 2-(2-methoxyethoxy)acetic acid (1), 2-(2-(2-methoxyethoxy)ethoxy)acetic acid (2), cyanoacetic acid (3), and benzoic acid (4); others were synthesized by reactions of GMA with diethyl hydrogen phosphate (5) or methanol (6). Monomers 1 and 2 are novel, 3 seems to be novel, 4 and 6 were synthesized via a novel method, and the synthesis of 5 was described in the literature. The monomers showed high crosslinking tendencies during thermal bulk polymerizations. The photo-, homo-, and copolymerization behavior of the monomers with 2,2-bis[4-(2-hydroxy-3-methacryloyloxy)phenyl]propane (Bis-GMA) were investigated. The maximum rate of polymerizations of monomers 2-6 was found to be greater than triethyleneglycol dimethacrylate, Bis-GMA, 2-hydroxyethyl methacrylate, and glycerol dimethacrylate. For the more reactive monomers (2, 3, and 4), the oxygen sensitivity of polymerization was found to be low due to a hydrogen abstraction/chain transfer reaction. The computationally calculated dipole moment and lowest unoccupied molecular orbital energies indicated that there seems to be a correlation between these quantities and reactivity for ester linked monomers (1-5), which was also supported by 13C NMR data.
- Karahan, Ozlem,Aydin, Kinyas,Edizer, Seda,Odabasi, Nihan,Avci, Duygu
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experimental part
p. 3787 - 3796
(2011/11/12)
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- Synthesis of the phosphonoanalogue of benzo[c]pyroglutamic acid
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Phosphonic analogue 1 of benzo[c]pyroglutamic acid was synthesized by three-step synthesis starting from N-tert-butylphtalimide and triethylphosphite. The acid-catalyzed, oxidative cascade conversion of phosphonate 11 to phthalimide and phosphoric acid diethyl ester was observed. A mechanism for this transformation was proposed. Taylor & Francis Group, LLC.
- Kachkovskyi, Georgiy O.,Kolodiazhnyi, Oleg I.
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experimental part
p. 2441 - 2448
(2011/02/25)
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