Quaternary Heteroarenium Aldoximes as Catalysts for Cleavage of Phosphate Esters

1995 ◽  
Vol 60 (5) ◽  
pp. 883-893 ◽  
Author(s):  
František Hampl ◽  
Jiří Mazáč ◽  
František Liška ◽  
Jiří Šrogl ◽  
Lubomír Kábrt ◽  
...  
Keyword(s):  
Aqueous Solutions ◽  
Critical Micellar Concentration ◽  
Considerable Effect ◽  
Phosphate Esters ◽  
Hexadecyltrimethylammonium Bromide ◽  
Hydrolytic Cleavage ◽  
Pseudo First Order Reaction ◽  
First Order ◽  
Diphenyl Phosphate ◽  
Hydrolysis Of

1-Methyl- (Ia - Id) and 1-dodecyl-2-, 3- and 4-hydroxyiminomethylpyridinium salts (Ie - Ih), as well as 1-methyl- (IIa) and 1-dodecyl-3-hydroxyiminomethylpyridazinium salts (IIb, IIc), were synthesized as catalysts for hydrolytic cleavage of organophosphates. The activities of the prepared catalysts were evaluated by measuring rate constants of hydrolysis of 4-nitrophenyl diphenyl phosphate (PNPDPP) under conditions of a pseudo-first-order reaction. The observed reactivity of pyridinium aldoximes Ia - Ih towards PNPDPP in neutral or slightly basic aqueous solutions (pH 7.2 and 7.8) depends on the acidity of the hydroxyimino group. The cleavage of PNPDPP is strongly accelerated in solutions of 1-dodecylhydroxyiminomethylpyridinium salts Ie - Ih above their critical micellar concentration (CMC). Considerable effect on the velocity of PNPDPP cleavage was observed when quaternary pyridinium aldoximes Ie - Ih were comicellized with inert cationic tenside hexadecyltrimethylammonium bromide (CTAB). 1-Dodecyl-3-hydroxyiminomethylpyridazinium salts IIb and IIc were unstable in aqueous solutions under the above-mentioned conditions.

Metal Ion Chelates of Lipophilic Alkyl Diazinyl Ketoximes as Hydrolytic Catalysts

1999 ◽  
Vol 64 (7) ◽  
pp. 1159-1179 ◽  
Author(s):  
Radek Cibulka ◽  
František Hampl ◽  
Tomáš Martinů ◽  
Jiří Mazáč ◽  
Sonja Totevová ◽  
...  
Keyword(s):  
Aqueous Solutions ◽  
Metal Ion ◽  
Hydrolytic Activity ◽  
Hexadecyltrimethylammonium Bromide ◽  
Diphenyl Phosphate ◽  
Hydrolysis Of ◽  
Metal Ligand

A series of lipophilic dodecyl hetaryl ketoximes (hetaryl = pyridin-2-yl, pyridazin-3-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrazin-2-yl as well as their methyl hetaryl homologues was synthesized and hydrolytic activity of their chelates with Co2+, Ni2+, Cu2+ and Zn2+ in a micellar matrix of hexadecyltrimethylammonium bromide or in homogeneous aqueous solutions was investigated using 4-nitrophenyl acetate, 4-nitrophenyl hexanoate and 4-nitrophenyl diphenyl phosphate as model substrates. While Co2+ and Cu2+ chelates are almost inactive, those of Ni2+ and Zn2+ exhibit considerable activity. None of the studied chelates promotes hydrolysis of the used phosphate. The effective species are chelates of the metal : ligand stoichiometry 1 : 3 and 1 : 1 with Ni2+ and Zn2+, respectively, when the ester cleavage proceeds in the micellar matrix. The 1 : 2 stoichiometry was found in aqueous solutions of Ni2+ and Zn2+ chelates of methyl ketoximes.

scholarly journals PHYSICAL CHEMICAL STUDIES OF THE SURFACTANT DILAURYLDIMETHYLAMMONIUM BROMIDE (DLDMAB): AGGREGATION AND CATALYTIC PROPERTIES

2009 ◽  
Vol 17 (17) ◽  
pp. 21-32
Author(s):  
Elizabeth Fatima de Souza ◽  
Silvia Dani ◽  
Lavinel G. IONESCU
Keyword(s):  
Thermodynamic Parameters ◽  
Catalytic Properties ◽  
Activation Parameters ◽  
Critical Micellar Concentration ◽  
Physical Chemical ◽  
Chemical Studies ◽  
Diphenyl Phosphate ◽  
C 32 ◽  
Free Energy Of Micellization ◽  
Hydrolysis Of

The micellization of dilauryldimethylammonium bromide (DLDMAB) in water was studied by using surface tension measurements. The critical micellar concentration (CMC) was determined at 25°C, 32°C and 40°C and thermodynamic parameters such as the free energy of micellization (∆G°mic), enthalpy (∆H°mic), and entropy (∆S°mic) of micellization were measured. The CMC at 25°C was 4.93 x 10-5 M and the corresponding values of the thermodynamic parameters were: ∆G°mic = -5.87 kcal/mol; ∆H°mic = -1.12 kcal/mol and ∆S°mic = +16.00 e.u. Micelles of the surfactant DLDMAB act as catalysts for the alkaline hydrolysis of p-nitrophenyl diphenyl phosphate (NPDPP) with a maximum catalytic factor of approximately 120 compared to 80 for CTAB. Typical activation parameters measured for 1.00 x 10-3 M surfactant and 0.005 M NaOH were: Ea = 9.7 kcal/mo/; ∆H°≠ = 9.1 kcal/mol; ∆G°≠ = 19.6 kcal/mol and ∆S°≠ = -33.9 e.u. The kinetic results were also analyzed in terms of the pseudo-phase ion-exchange models (PPIE) and showed that the model is applicable to describe the experimental results.

Effect of Cyclodextrins on Photodegradation of 4,4-Bis(4-Hydroxyphenyl)Pentanoic Acid under UV Irradiation

2014 ◽  
Vol 665 ◽  
pp. 455-458
Author(s):  
Li Guo ◽  
Jin Huang ◽  
Jun Wu ◽  
Lei Lei Luo
Keyword(s):  
Aqueous Solutions ◽  
Fluorescence Spectra ◽  
High Efficiency ◽  
Uv Light ◽  
Order Reaction ◽  
Pentanoic Acid ◽  
Pseudo First Order Reaction ◽  
First Order ◽  
Inclusion Interaction ◽  
Pseudo First Order

The photodegradation of 4,4-bis (4-hydroxyphenyl) pentanoic acid (DPA) with two cyclodextrins (α-CD and β-CD ) in aqueous solutions induced by UV-light was studied in this paper by means of fluorescence spectra and high efficiency liquid chromatography. The result suggested that DPA with α-CD or β-CD formed inclusion compound in aqueous solutions. The photodegradation of DPA with two cyclodextrins or without cyclodextrin was pseudo-first order reaction. The photodegradation of DPA was accelerated by the addition of β-CD in aqueous solutions, but the that of DPA was inhibited in case of adding α-CD. These differences were due to the differences in inclusion interaction of DPA with α-CD or β-CD.

scholarly journals PHYSICAL CHEMICAL STUDIES OF THE AGGREGATION AND CATALYTIC PROPERTIES OF THE SURFACTANT CETYLDIMETHYLETHYLAMMONIUM BROMIDE (CDEAB)

1999 ◽  
Vol 7 (8) ◽  
pp. 105-114
Author(s):  
Lavinel G. Ionescu ◽  
Silvia Dani ◽  
Elizabeth Fatima de Souza
Keyword(s):  
Free Energy ◽  
Catalytic Properties ◽  
Activation Parameters ◽  
Critical Micellar Concentration ◽  
Physical Chemical ◽  
Chemical Studies ◽  
Diphenyl Phosphate ◽  
Free Energy Of Micellization ◽  
Surface Tensiometry ◽  
Hydrolysis Of

The micellization of cetyldimethylethylammonium bromide (CDEAB) in water was studied by means of surface tensiometry. The critical micellar concentration (CMC) was determined at 25°, 32°, and 40°C, and thermodynamic properties such as the free energy of micellization (∆G°mic), enthalpy (∆H°mic) and entropy (∆S°mic) of micellization were measured. The CMC at 25°C was 9.05 x 10-4 M and the corresponding values of the thermodynamic parameters were: ∆G°mic = -4.15 kcal/mol; ∆H°mic = -1.37 kcal/mol and ∆S°mic = + 9.33 e.u. Micelles of the surfactant CDEAB were good catalysts for the alkaline hydrolysis of p-nitrophenyl diphenyl phosphate (NPDPP) with a maximum catalytic factor of approximately 80, comparable to that of CTAB. Typical activation parameters measured for 0.005 M NaOH were: Ea = 9.0 kcal/mol; ∆H°≠ = 8.4 kcal/mol; ∆G°≠ = 19.2 kcal/mol and ∆S°≠ = -36.3 e.u. The kinetic results were also analyzed in terms of the pseudo-phase ion-exchange models (PPIE) and showed that the model is applicable and gave reasonable fits

scholarly journals Involvement of an arginyl residue in the nucleotide-binding site of Ca2+-ATPase from sarcoplasmic reticulum as seen by reaction with phenylglyoxal

1996 ◽  
Vol 318 (1) ◽  
pp. 179-185
Author(s):  
Senena CORBALÁN-GARCÍA ◽  
José A. TERUEL ◽  
Juan C. GÓMEZ-FERNÁNDEZ
Keyword(s):  
Atpase Activity ◽  
Calcium Binding ◽  
Reaction Medium ◽  
Order Rate Constant ◽  
Inhibition Mechanism ◽  
Pseudo First Order Reaction ◽  
First Order ◽  
Arginine Residues ◽  
Atpase Inhibition ◽  
Hydrolysis Of

1. Chemical modification of the Ca2+-ATPase with phenylglyoxal, as a modifier of arginine residues, leads to an almost total loss of the ATPase activity. The presence of nucleotides in the reaction medium protects against the binding of 18 nmol of phenylglyoxal/mg of protein and this reduction in the binding of phenylglyoxal is accompanied by a substantial retention of ATPase activity. The incorporation of phenylglyoxal to the protein alters neither calcium binding nor phosphorylation from inorganic phosphate. Nevertheless the binding of nucleotides is dramatically inhibited and, consequently, so is phosphorylation from ATP. Fluorescein 5´-isothiocyanate labelling of the phenylglyoxal-modified ATPase is not affected but, on the other hand, phenylglyoxal is not able to modify the fluorescein 5´-isothiocyanate-prelabelled ATPase. The way in which ATPase inhibition depends on the presence of phenylglyoxal indicates that this process occurs in a pseudo-first-order reaction. However, the dependence of the apparent first-order rate constant on phenylglyoxal concentration appears to be more complex and an inhibition mechanism of two steps, with phenylglyoxal binding, has to be taken into account. 2. We have found that phenylglyoxal labels both A and B tryptic fragments, but only B fragment labelling is prevented by ATP. The sequencing of peptides from mild acid hydrolysis of phenylglyoxal-labelled ATPase shows that phenylglyoxal is located in the Ala506–Gly595 peptide that is a part of the B fragment. 3. We conclude that phenylglyoxal inactivates the calcium pump in a two-step mechanism in which the second step is irreversible. Phenylglyoxal labels an arginyl residue in the Ala506–Gly595 peptide that can be protected by the binding of ATP to its site.

Catalytic hydrolysis of phosphate esters in microemulsions. 3. Analysis of the hydrolysis products of p-nitrophenyl diphenyl phosphate via 31P NMR

1988 ◽  
Vol 53 (9) ◽  
pp. 2009-2011 ◽  
Author(s):  
Beth A. Burnside ◽  
Linda L. Szafraniec ◽  
Barry L. Knier ◽  
H. Dupont Durst ◽  
Raymond A. Mackay ◽  
...  
Keyword(s):  
31P Nmr ◽  
Phosphate Esters ◽  
Catalytic Hydrolysis ◽  
Hydrolysis Products ◽  
Diphenyl Phosphate ◽  
Hydrolysis Of

Metallomicellar Hydrolytic Catalysts Containing Ligand Surfactants Derived from Alkyl Pyridin-2-yl Ketoxime

1997 ◽  
Vol 62 (8) ◽  
pp. 1342-1354 ◽  
Author(s):  
Radek Cibulka ◽  
David Dvořák ◽  
František Hampl ◽  
František Liška
Keyword(s):  
Metal Ion ◽  
Transition Metal Ions ◽  
Water Soluble ◽  
Hexadecyltrimethylammonium Bromide ◽  
Pseudo First Order Reaction ◽  
Reaction Conditions ◽  
Catalytic Systems ◽  
First Order ◽  
Substrate Cleavage ◽  
Kinetics Of

N-Hexyl- (2a), N-octyl- (2b), N-decyl- (2c) and N-dodecyl-N-[2-(hydroxyimino)-2-(pyridin-2-yl)ethyl]dimethylammonium (2d) nitrates were synthesized as water-soluble cationic ligand surfactants. Three types of micellar catalytic systems employing salts 2 were prepared: homomicellar water solutions of salts 2, comicellar solutions of salts 2 with an inert cationic tenside hexadecyltrimethylammonium bromide (CTAB) and comicellar systems consisting of complexes of ligand surfactants 2 with transition metal ions (Co(II), Ni(II), Cu(II) and Zn(II)) and CTAB. Hydrolytic efficiency of all micellar and metallomicellar systems was tested by measuring the kinetics of the model substrate cleavage under pseudo-first-order reaction conditions. Of the above-mentioned catalysts, comicellar systems of salts 2 comicellized with CTAB were most efficient. In all cases, with the exception of Zn(II), coordination of a metal ion decreased the hydrolytic efficiency of salts 2.

scholarly journals Catalytically Active Gold Nanoparticles Synthesized using Diabetic Sugar Via Rapid, Simple, Greener Process

2019 ◽  
Vol 35 (5) ◽  
pp. 1519-1528
Author(s):  
Nurdiani Nurdiani ◽  
Foliatini Foliatini
Keyword(s):  
Reaction Rate ◽  
Au Nanoparticles ◽  
Colloidal Solution ◽  
Oxidation Process ◽  
Infrared Spectrophotometry ◽  
Pseudo First Order Reaction ◽  
First Order ◽  
Catalytically Active ◽  
Kinetics Of ◽  
Hydrolysis Of

Au nanoparticles were successfully synthesized using diabetic sugar as reducing agent, with and without the aid of microwave heating. The hydrolysis of diabetic sugar was carried out using HCl, prior to the synthesis. By adjusting pH of the mixture to basic condition, the formation of the nanoparticles effectively occurred resulting purple colloidal solution. The solution was centrifuged or left overnight to yield precipitate of Au nanoparticles. The as-formed Au nanoparticles were characterized by UV-Vis spectrophotometry, Fourier-Transform infrared spectrophotometry and scanning electron microscopy. The result showed that the Au nanoparticles played a significant role as catalyst for oxidation of methylene blue by H2O2. The kinetics of the oxidation process followed pseudo first order reaction rate with the rate constant depending on the AuNP characteristic and experimental condition.

Sign in / Sign up

Export Citation Format

Share Document