14609-74-6Relevant articles and documents
Thermodynamic origin of the increased rate of hydrolysis of phosphate and phosphorothioate esters in DMSO/water mixtures
Sorensen-Stowell, Kerensa,Hengge, Alvan C.
, p. 7180 - 7184 (2006)
The hydrolysis rates of the dianions of phosphate and phosphorothioate esters are substantially accelerated by the addition of polar aprotic solvents such as DMSO and acetonitrile. The activation barrier ΔG? is smaller due to a lower enthalpy of activatio
Cetylpyridinium bromide-based oil-in-water microemulsions as a medium for hydrolysis of esters of phosphorus acids in the presence of primary amines
Mirgorodskaya,Kudryavtseva,Zuev,Idiyatullin,Fedotov
, p. 245 - 249 (2001)
High-resolution 1H NMR technique with Fourier-transform and pulsed-gradient spin-echo was used to study the structure of oil-in-water microemulsions based on cetylpyridinium bromide. The sizes of microdrops and the distribution of components between the disperse and continuous phases were found. It was shown for the hydrolytic decomposition of O,O-bis-(p-nitrophenyl) methyl phosphonate in the presence of amines that the microemulsion medium can affect both the rate and mechanism of hydrolysis. The reaction rate constants depend on the structure of microdrops.
Synthesis and phosphatase activity of a Cobalt(II) phenanthroline complex
Garai, Mamoni,Dey, Dhananjay,Yadav, Hare Ram,Maji, Milan,Choudhury, Angshuman Roy,Biswas, Bhaskar
, p. 1513 - 1520 (2017)
Abstract: A mononuclear cobalt(II) complex, [Co (phen) 2Cl 2], (phen = 1,10-phenanthroline) has been synthesized and structurally characterized by different spectroscopic methods including single crystal X-ray structural study. X-ray
A study on a primitive artificial esterase model: Reactivity of a calix[4]resorcinarene bearing carboxyl groups
Cevasco, Giorgio,Galatini, Andrea,Pirinccioglu, Necmettin,Thea, Sergio,Williams, Andrew
, p. 498 - 504 (2008)
The host molecule octacarboxymethyl calix[4]resorcinarene 1 catalyses the hydrolysis of substituted phenyl N-methylpyridinium-4-carboxylate esters 3a-f by complexation followed by intracomplex reaction via an anhydride intermediate. The reactivity in the
Structural, electrochemical, phosphate-hydrolysis, DNA binding and cleavage studies of new macrocyclic binuclear nickel(ii) complexes
Anbu, Sellamuthu,Kandaswamy, Muthusamy,Varghese, Babu
, p. 3823 - 3832 (2010)
New macrocyclic binuclear nickel(ii) complexes have been synthesized by using the bicompartmental mononuclear complex [NiL] [3,30-((1E,7E)-3,6-dioxa-2, 7-diazaocta-1,7-diene-1,8-diyl)bis(3-formyl-5-methyl-2-diolato)nickel(ii)] with various diamines like 1
POLYMER-BOUND IODOSOBENZOATE REAGENTS FOR THE CLEAVAGE OF REACTIVE PHOSPHATES
Moss, Robert A.,Bolikal, Durgadas,Durst, H. Dupont,Hovanec, Joseph W.
, p. 2433 - 2436 (1988)
Two polymer-bound iodosobenzoate derivatives have been prepared and found to be phosphorolytically active against both p-nitrophenyldiphenyl phosphate and the nerve agent, Soman.
Development of a lipase-based optical assay for detection of DNA
Pinijsuwan, Suttiporn,Shipovskov, Stepan,Surareungchai, Werasak,Ferapontova, Elena E.,Gothelf, Kurt V.
, p. 6352 - 6356 (2011)
A lipase-based assay for detection of specific DNA sequences has been developed. Lipase from Candida antarctica was conjugated to DNA and captured on magnetic beads in a sandwich assay, in which the binding was dependent on the presence of a specific target DNA. For amplification and to generate a detectable readout the captured lipase was applied to an optical assay that takes advantage of the enzymatic activity of lipase. The assay applies p-nitrophenol octanoate (NPO) as the substrate and in the presence of lipase the ester is hydrolyzed to p-nitrophenolate which has a strong absorbance at 405 nm. The method provides detection a detection limit of 200 fmol target DNA and it was able to distinguish single base mismatches from the fully complementary target.
Polypeptides with supersecondary structures as templates in rational catalyst design. Catalysis of self functionalization by designed helix-loop-helix motifs
Baltzer, Lars,Lundh, Ann-Christin,Broo, Klas,Olofsson, Susanne,Ahlberg, Per
, p. 1671 - 1676 (1996)
Three designed polypeptides with 42 amino acids each, SA-42, RA-42 and PA-42, were engineered to catalyse acyl-transfer reactions of mono-p-nitrophenylfumarate I. The second-order rate constants of the peptides for the formation of p-nitrophenol were larger than that of the background reaction with factors of 331, 1750 and 1937, respectively. The background reaction is the reaction between I and trifiuoroethoxide ion to form the trifluoroethyl ester. The second-order rate constant for the 4-methylimidazole catalysed reaction between I and trifluoroethoxide ion was 211 times larger than that of the background reaction and the similarity in rate constants suggests that the histidine residues in the polypeptides act as nucleophilic catalysts. The observed rate increases in RA-42 and PA-42 over that of SA-42 identifies the location of the reaction centre. The identity of the reaction products in the RA-42 catalysed reaction was established by NMR spectroscopy and mass spectrometry. The side chain of ornithine-15 was acylated by the fumaryl residue. Thus, in a fast and selective second reaction step the fumaryl group was transferred from histidine-11 to the side chain of ornithine-15. The ability of a designed helix-loop-helix motif, RA-42, to catalyse its own functionalization is thereby demonstrated for the first time.
Phosphodiester cleavage by trivalent lanthanides in the presence of native cyclodextrins
Ruiz Kubli, Mariel,Yatsimirsky, Anatoly K.
, p. 9 - 15 (2016)
Testing phosphodiesterase activity of Eu(III) in the presence of native cyclodextrins revealed capacity of β-cyclodextrin (β-CD) to stabilize catalytically active metal hydroxocomplexes in mildly basic solutions. Kinetics of the hydrolysis of bis(4-nitrop
Coordination sphere of the third metal site is essential to the activity and metal selectivity of alkaline phosphatases
Koutsioulis, Dimitris,Lyskowski, Andrzej,Maeki, Seija,Guthrie, Ellen,Feller, Georges,Bouriotis, Vassilis,Heikinheimo, Pirkko
, p. 75 - 84 (2010)
Alkaline phosphatases (APs) are commercially applied enzymes that catalyze the hydrolysis of phosphate monoesters by a reaction involving three active site metal ions. We have previously identified H135 as the key residue for controlling activity of the p
Single-electron oxidation and nucleophilicity of aminomethylated calix[4]resorcinarenes
Yanilkin,Ryzhkina,Nastapova,Pashirova,Babkina,Burilov,Morozov,Konovalov
, p. 1142 - 1149 (2003)
The electrochemical oxidation of a number of aminomethylated calix[4]resorcinarenes (AMC) with different substituents at the nitrogen atom and the kinetics of nucleophilic substitution reactions of these compounds with p-nitrophenyl bis(chloromethyl)phosphinate were studied. The reactivity of the ionic associates of AMC in the nucleophilic substitution and the behavior of AMC in electrooxidation are determined by the same factors, namely, the amino-group basicity and the nature of the substituents at the nitrogen atom. These factors influence the ratio of the zwitter-ionic and anionic forms of AMC.
Phosphatase models: Synthesis, structure and catalytic activity of zinc complexes derived from a phenolic Mannich-base ligand
Sanyal, Ria,Chakraborty, Prateeti,Zangrando, Ennio,Das, Debasis
, p. 55 - 65 (2015)
A series of dinuclear [Zn2(L1)2X2] (1-3) and mononuclear [Zn(HL2)X2] complexes (4-6), (X = Cl, Br, I) were synthesised from two Mannich-base compartmental ligands, namely [bis(2-methoxyethyl)aminomethyl]-4-chlor
Physical and kinetic analysis of the cooperative role of metal ions in catalysis of phosphodiester cleavage by a dinuclear Zn(II) complex
Iranzo, Olga,Kovalevsky, Andrey Y.,Morrow, Janet R.,Richard, John P.
, p. 1988 - 1993 (2003)
A dinuclear metal ion complex Zn2(L20) and its mononuclear analogue Zn(L10H) were synthesized and studied as catalysts of the cleavage of the phosphate diester 2-hydroxypropyl-4-nitrophenyl phosphate (HPNP). X-ray crystal structure data, potentiometric titrations, and 1H NMR spectra obtained over a wide range of pH values provide strong evidence that the alcohol linker in the complex Zn2(L20) is ionized below pH 6.0, while the alcohol group in the complex Zn(L10H) remains protonated even at high pH. The ionizations observed at high pH correspond to the formation of the monohydroxo complexes, Zn2(L20)(OH) and Zn(L10H)(OH), with pKa's of 8.0 and 9.2, respectively. The pH-rate profiles of second-order rate constants for metal-ion complex-catalyzed cleavage of HPNP are reported. These show downward curvature centered at the pKa's for the respective zinc-bound waters, and limiting second-order rate constants at high pH of kc = 0.71 M-1 s-1 for Zn2(L20) and 0.061 M-1 s-1 for Zn(L10H). The larger catalytic activity of Zn2(L20) compared with Zn(L10H) is due to the cooperative role of the metal ions in facilitating the formation of the ionized zinc-bound water at close to neutral pH and in providing additional stabilization of the rate-limiting transition state for phosphodiester cleavage. Zn2(L20) complex (1 M) at pH 7.6 stabilizes the transition state for the uncatalyzed reaction by 9.3 kcal/mol. Assuming that the dissociation constant determined for a diethyl phosphate inhibitor is similar to that for substrate, then ca. 2.4 kcal/mol of these stabilizing interactions are expressed in the ground-state Michaelis complex, while the bulk of these interactions are only expressed as the reaction approaches the transition state for phosphodiester cleavage.
Kinetic study on aminolysis of aryl X-substituted-cinnamates in acetonitrile: Differential medium effect determines reactivity and reaction mechanism
Um, Ik-Hwan,Bae, Ae-Ri,Dust, Julian M.
, p. 13 - 19 (2019)
A kinetic study on nucleophilic substitution reactions of 2,4-dinitrophenyl X-substituted-cinnamates (1a-1f) and Y-substituted-phenyl cinnamates (2a-2g) with a series of alicyclic secondary amines in MeCN at 25.0 ± 0.1 °C is reported. The Br?nsted-type pl
Cyclen based lanthanide ion ribonuclease mimics: The effect of pyridine cofactors upon phosphodiester HPNP hydrolysis
Gunnlaugsson, Thorfinnur,Davies, R. Jeremy H.,Kruger, Paul E.,Jensen, Paul,McCabe, Thomas,Mulready, Sinead,O'Brien, John E.,Stevenson, Clarke S.,Fanning, Ann-Marie
, p. 3761 - 3766 (2005)
The cyclen based pyridine complexes 1Ln-3Ln (Ln = La(III) and Eu(III)) were synthesised as metallo-ribonuclease mimics and their ability to hydrolytically cleave the phosphodiester of HPNP at 37°C was investigated using UV-vis spectroscopy, whereas the bi
Dissection of activation parameters in the bell-shaped α-effect following solvent modulation (DMSO-H2O Media)
Um, Ik-Hwan,Kang, Ji-Sun,Kim, Min-Young,Buncel, Erwin
, p. 8689 - 8695 (2013)
This paper comprises results of our investigation of the α-effect phenomenon for the reaction of O-p-nitrophenyl thionobenzoate (PNPTB) with butane-2,3-dione monoximate (Ox-, α-nucleophile) and p-chlorophenoxide (p-ClPhO-, normal-nucleophile) in DMSO-H 2O mixtures of varying compositions at 15.0 C, 25.0 C, and 35.0 C. The reactivity of Ox- and p-ClPhO- increases significantly as the DMSO content in the medium increases, although the effects of medium on reactivity are not the same for the reactions with Ox- and p-ClPhO-. Ox- exhibits the α-effect in all solvent compositions and temperatures. The α-effect increases up to 50 mol % DMSO and then decreases thereafter, resulting in a bell-shaped α-effect profile. Dissection of the activation parameters (i.e., ΔH a and TΔSa) has revealed that the bell-shaped α-effect behavior is due to entropy of activation differences rather than enthalpy terms, although the enthalpy term controls almost entirely the solvent dependence of the reaction rate. Differences in the transition-state (TS) structures for the reactions with Ox- (a six-membered cyclic TS) and p-ClPhO- (an acyclic TS) are consistent with the entropy-dependent α-effect behavior.
Structure and properties of water-oil microemulsions
Mirgorodskaya,Kudryavtseva,Zuev,Idiyatullin,Fedotov
, p. 1007 - 1011 (2002)
The parameters determining the structure and properties (surface potential and size of microdrops) of oil-water microemulsions containing various surfactants, and also the distribution of components between the dispersed phase and dispersing medium were d
Phosphate diesters and DNA hydrolysis by dinuclear Zn(II) complexes featuring a disulfide bridge and H-bond donors
Lombardo, Valentina,Bonomi, Renato,Sissi, Claudia,Mancin, Fabrizio
, p. 2189 - 2195 (2010)
The dinuclear ligand 1 based on the bis-(2-amino-pyridinyl-6-methyl)amine (BAPA) metal binding unit and featuring a two-atom disulfide bridge was synthesized and studied as hydrolytic catalysts for phosphate diesters. The Zn(II) complexes of BAPA are know
The salt effect in the alkaline hydrolysis of O-ethyl O-(p-nitrophenyl) chloromethylphosphonate catalyzed by cetylpyridinium bromide
Zakharova,Kudryavtseva,Konovalov
, p. 1868 - 1872 (1998)
The alkaline hydrolysis of O-ethyl O-(p-nitrophenyl) chloromethylphosphonate catalyzed by the micelles of cetylpyridinium bromide is inhibited on addition of KCl, KBr, or sodium salicylate (NaSal). This is caused by both a decrease in the nucleophile concentration in micelles owing to a reduction in the surface potential and a change in the micellar structure and properties.
Effect of Pressure on the Pre-Steady-State Kinetics of the Hydrolysis of p-Nitrophenyl Pivalate Catalyzed by α-Chymotrypsin
Makimoto, Syoichi,Suzuki, Keizo,Taniguchi, Yoshihiro
, p. 243 - 248 (1986)
The pre-steady-state of the hydrolysis of p-nitrophenyl pivalate (pNPT) catalyzed by α-chymotropsyn (α-CHT) in Tris buffer solutions was measured up to 2.4 k bar at 25 deg C.The reaction was initiated by substrate binding, and followed by acylation and de
Synthesis and phosphodiester transesterification activity of the La3+- complex of a novel functionalized octadentate ligand
Baykal, Ulku,Akkaya, Engin U.
, p. 5861 - 5864 (1998)
Various lanthanide complexes have been shown to promote phosphodiester hydrolysis. Distribution of the available coordination sites of the lanthanides between the ligand and the labile water molecules has proved to be critical in determining the activity and stability of the complex in water at neutral pH. Since the final goal is to conjugate such hydrolytically active molecules to DNA oligomers, the design must include a functionality that can be made reactive in standard conjugation protocols. To that end, we have synthesized a nitrophenyl-derivatized TCMC-La3+ complex, and it is as active as the unmodified TCMC-La3+ in the transesterification of an RNA model substrate.
Kinetics of alkaline hydrolysis of ethyl p-nitrophenyl ethylphosphonate in the reverse micellar system: Sodium dodecyl sulfate-hexanol-water
Zakharova,Valeeva,Kudryavtseva,Bel'skii,Zhil'tsova,Zakharchenko,Zuev
, p. 265 - 269 (2000)
The kinetics of alkaline hydrolysis of ethyl p-nitrophenyl ethylphosphonate in the reverse micellar system sodium dodecyl sulfate-hexanol-water was studied. At high pH and low water content, the process occurs at the surface layer and can satisfactorily b
Stability of 1:1 and 2:1 α-cyclodextrin-p-nitrophenyl acetate complexes and the effect of α-cyclodextrin on acyl transfer to peroxide anion nucleophiles
Davies, D. Martin,Deary, Michael E.
, p. 1027 - 1034 (1999)
The presence of a rate maximum rather than simple saturation-type kinetics in a study of the effect of α-cyclodextrin on the hydrolysis of p-nitrophenyl acetate (PNPA) indicates that α-cyclodextrin forms not only 1:1 but also 2:1 complexes with PNPA. This is confirmed using a spectrophotometric method to determine binding constants directly for PNPA, giving values of 46 ± 9 and 66 ± 19 dm3 mol-1 for the first and second binding steps respectively. These results contradict the majority of literature studies of this reaction in which it is assumed that only a 1:1 complex is formed. Formation of a 1 :1 complex with cyclodextrin increases the reactivity of PNPA towards hydrolysis, as has been widely reported, whereas the addition of a second cyclodextrin molecule to the complex results in the PNPA taking up a less reactive configuration. The effect of α-cyclodextrin on the reaction between PNPA and the anions of hydrogen peroxide, peroxomonosulfate, peracetic acid, perbenzoic acid, 4-methylperbenzoic acid, 4-nitroperbenzoic acid, 4-sulfonatoperbenzoic acid, 3-chloroperbenzoic acid and 4-tert-butylperbenzoic acid is described. Linear free energy studies for transition state stabilisation of the reaction by one molecule of cyclodextrin reveal that the main pathway involves the bound PNPA reacting with free peroxide anions, although for m-chloroperbenzoic acid an alternative pathway may be significant. This is in contrast to the behaviour observed for the α-cyclodextrin-mediated reaction of the molecular acid form of these peroxides with a series of aryl alkyl sulfides in which the main pathway involves nucleophilic attack of the free sulfide on the cyclodextrin-peracid complex. With the exception of the m-chloroperbenzoic acid anion there is no evidence of transition state stabilisation of the title reaction by two molecules of cyclodextrin.
Carbonic Anhydrase Models. 4. phosphine oxide>cobalt(2+); A Small-Molecule Mimic of the Spectroscopic Properties of Co(II) Carbonic Anhydrase
Brown, R. S.,Salmon, D.,Curtis, N. J.,Kusuma, S.
, p. 3188 - 3194 (1982)
The title compound when bound to Zn(II) or Co(II) displays many properties in common with carbonic anhydrase.These include a weak ability of the Zn(II) complex to catalyze the interconversion of CO2 and HCO3(-) and anion-dependent visible absorption spect
Conformational Effect (Induced-Fit) on Catalytic Activity of α-Chymotrypsin
Kawai, Yasushi,Matsuo, Takashi,Ohno, Atsuyoshi
, p. 2187 - 2196 (1998)
The kinetics for the hydrolyses of p-nitrophenyl esters of acetic acid and certain amino acid derivatives mediated by α-chymotrypsin have been studied. The kinetics are a function of the medium viscosity, which indicate that the enzyme must change its con
Homodinuclear copper(II) and zinc(II) complexes of a carboxylate-rich ligand as synthetic mimics of phosphoester hydrolase in aqueous solutions
Foley, William,Arman, Hadi,Musie, Ghezai T.
, (2021/09/14)
The synthesis, characterization and catalytic activities of two homodinuclear Cu(II) and Zn(II) complexes of a carboxylate-rich ligand, N,N′-Bis[2-carboxybenzomethyl]-N,N′ -Bis[carboxymethyl]-1,3-diaminopropan-2-ol (H5ccdp) ligand towards the h
Mono- and dinuclear zinc complexes bearing identical bis(thiosemicarbazone) ligand that exhibit alkaline phosphatase-like catalytic reactivity
Cho, Kyung-Bin,Hong, Seungwoo,Jeon, Hyeri,Jeong, Haewon,Vazquez-Lima, Hugo
, (2021/11/08)
Mono- and dinuclear zinc(II) complexes bearing bis(thiosemicarbazone) (bTSC) ligand were employed in the cleavage of phosphoester bonds. Comparative kinetic studies combined with theory suggested that the P–O bond cleavage is much accelerated by dinuclear
Soft nanosystems based on hydroxypiperidinium surfactants as adjuvants and micellar catalysts
Kushnazarova, Rushana A.,Lukashenko, Svetlana S.,Mirgorodskaya, Alla B.,Sinyashin, Oleg G.,Tyryshkina, Anna A.,Valeeva, Farida G.,Zakharova, Lucia Ya.
, p. 323 - 325 (2021/06/07)
Quantitative parameters characterizing aggregation behaviour and wetting effect of 1-(2-hydroxyethyl)-piperidinium surfactants have been obtained. Their ability to act as adjuvants in herbicidal compositions based on clopyralid has been revealed. The kine
