Metal Ion Catalysis in the Hydrolysis of Esters of 2-Hydroxy-1,10-phenanthroline: The Effects of Metal Ions on Intramolecular Carboxyl Group Participation

Fife, Thomas H.; Pujari, Mahesh P.

doi:10.1006/bioo.2000.1176

Cited by 24 publications

(7 citation statements)

References 36 publications

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“…Metal ions have been shown to influence the rate of hydrolysis of organic compounds where some these reactions show pH dependence , and others do not . Some of these reactions represent metal ion promoted OH – − and H + , catalyzing hydrolysis of esters. The promotion effect of divalent metal ion in the OH – hydrolysis of esters has been reported to have the rate enhanced up to 90–10 9 times. ,,− Typically, metal ion promoted OH – catalyzed reactions have been observed in ester hydrolysis reaction, when there is a functional group present in the ester which will allow strong interaction with the metal ions that will lead to chelation. − ,− This can also be favored by using high metal-to-ligand ratios. , Nucleophilic attack of the OH – is made easy due to the polarization of the carbonyl oxygen by metal ions .…”

Section: Resultsmentioning

confidence: 99%

New Route to Polynuclear Ni(II) and Cu(II) Complexes with Bridging Oxime Groups That Are Inaccessible by Conventional Preparations

Opalade

Gómez‐García

Gerasimchuk

2019

Crystal Growth & Design

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A series of new polynuclear complexes of divalent Ni and Cu with 2-cyano-2-oximino-acetic acid (later AACO2-) were obtained as the result of the ligand modification reaction in the process of complexation, using 2-cyano-2-oximino-acetates such as methyl- (later as MeCO), and ethyl- (as ECO later on). Synthesized compounds were characterized by spectroscopic methods, thermal analysis, magnetochemistry, and X-ray crystallography. Crystal data revealed the formation of the dimeric [Ni(AACO)(H2O)3]2·H2O (1), trimeric K2[Ni3(AACO)4(H2O)4]·4H2O (2), and K2[Cu3(AACO)4(H2O)4]·4H2O (3) complexes, with bridging NO-groups cyanoxime dianions. In the latter two compounds, the AACO2– anions adopt cis-arrangements around metal centers. One mononuclear complex of K2[Cu(AACO)2(H2O)]·2H2O (4) composition was isolated and characterized as well, where the cyanoxime forms the trans-complex 4. There is moderate-to-strong antiferromagnetic coupling between metal centers in polynuclear complexes. Data of thermal analysis studies revealed high-energy properties for dehydrated complexes 3 and 4, which violently decompose at ∼200 °C. These compounds may be viewed as room temperature completely safe, but heat-triggered actuators, because of their pronounced mechanical action upon leaving the system (crucible). Final products of thermal decomposition are Ni and NiO for 1, and the mixture of NiO and K2O for 2, with metallic copper for 3 and 4.

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Section: Resultsmentioning

confidence: 99%

New Route to Polynuclear Ni(II) and Cu(II) Complexes with Bridging Oxime Groups That Are Inaccessible by Conventional Preparations

Opalade

Gómez‐García

Gerasimchuk

2019

Crystal Growth & Design

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“…In fact, the crystal structures do not suggest any other putative amino acid residues, which would, for example, promote a nucleophilic attack of water to the carbonyl carbon. According to the literature, divalent metal ions alone are able, at least weakly, to catalyze the ester bond hydrolysis 13‐16 . Consequently, it might be possible that by the formation of a substrate–enzyme complex, the lifetime of otherwise weak association of Fe 2+ and the carbonyl oxygen increases considerably in appropriate orientations.…”

Section: Resultsmentioning

confidence: 99%

“…The images were processed to 2.8 Å resolution with XDS program package, 23 and using this data file, calculations were done with PHENIX software suite 24 . Using the homologous mouse SMP30 gluconolactonase (PDB entry http://firstglance.jmol.org/fg.htm?mol=4GN7) 16 as the initial model, molecular replacement was done with MR‐Rosetta 25 and Phaser 26 . Extensive manual editing of the model with Coot 27 and structure refinement with phenix.refine 28 resulted in a model, which contained few water molecules and lacked any ligands but could be used as an initial model for future calculations.…”

Section: Methodsmentioning

confidence: 99%

“…See the text for more details alone are able, at least weakly, to catalyze the ester bond hydrolysis. [13][14][15][16] Consequently, it might be possible that by the formation of a substrate-enzyme complex, the lifetime of otherwise weak association of Fe 2+ and the carbonyl oxygen increases considerably in appropriate orientations. This in turn would allow a weak nucleophile, a water molecule, to attack and initiate the intramolecular ester bond hydrolysis reaction.…”

Section: Reaction Mechanismmentioning

confidence: 99%

“…The images were processed to 2.8 Å resolution with XDS program package, 23 and using this data file, calculations were done with PHENIX software suite. 24 Using the homologous mouse SMP30 gluconolactonase (PDB entry 4GN7) 16 as the initial model, molecular replacement was done with MR-Rosetta 25 and Phaser. 26 Extensive manual editing of the model with Coot 27 and structure refinement with phenix.…”

Section: Structure Determinationmentioning

confidence: 99%

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Three‐dimensional structure of xylonolactonase from Caulobacter crescentus: A mononuclear iron enzyme of the 6‐bladed β‐propeller hydrolase family

et al. 2021

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Xylonolactonase Cc XylC from Caulobacter crescentus catalyzes the hydrolysis of the intramolecular ester bond of D-xylonolactone. We have determined crystal structures of Cc XylC in complex with D-xylonolactone isomer analogues Dxylopyranose and (R)-(+)-4-hydroxy-2-pyrrolidinone at high resolution. Cc XylC has a 6-bladed β-propeller architecture, which contains a central open channel having the active site at one end. According to our previous native mass spectrometry studies, Cc XylC is able to specifically bind Fe 2+ . The crystal structures, presented here, revealed an active site bound metal ion with an octahedral binding geometry. The side chains of three amino acid residues, Glu18, Asn146, and Asp196, which participate in binding of metal ion are located in the same plane.The solved complex structures allowed suggesting a reaction mechanism for intramolecular ester bond hydrolysis in which the major contribution for catalysis arises from the carbonyl oxygen coordination of the xylonolactone substrate to the Fe 2+ . The structure of Cc XylC was compared with eight other ester hydrolases of the β-propeller hydrolase family. The previously published crystal structures of other β-propeller hydrolases contain either Ca 2+ , Mg 2+ , or Zn 2+ and show clear similarities in ligand and metal ion binding geometries to that of Cc XylC. It would be interesting to reinvestigate the metal binding specificity of these enzymes and clarify whether they are also able to use Fe 2+ as a catalytic metal. This could further expand our understanding of utilization of Fe 2+ not only in oxidative enzymes but also in hydrolases.

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S_NAr Reactions of 1‐Halo‐2,4‐dinitrobenzenes with Alkali‐Metal Ethoxides: Differential Stabilization of Ground State and Transition State Determines Alkali‐Metal Ion Catalysis or Inhibition

Yang

Kim

2015

Bulletin Korean Chem Soc

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A kinetic study on S N Ar reactions of 1-halo-2,4-dinitrobenzenes (6a-6d) with alkali-metal ethoxides (EtOM; M = Li, Na, K and 18-crown-6-ether-complexed K) is reported. The plots of pseudo-first-order rate constant (k obsd ) vs.[EtOM] curve upward or downward depending on the size of M + ions. The reactions are catalyzed or inhibited by the M + ions, e.g., the large K + ion complexed by 18-crown-6-ether (18C6) acts as a catalyst while the small Li + and Na + ions behave as an inhibitor. Reactivity of 6a-6d toward EtOM decreases linearly as the halide ion becomes less basic regardless of the size of M + ions, indicating that expulsion of the leaving group occurs after the rate-determining step (RDS). Thus, the reactions have been proposed to proceed through a stepwise mechanism with formation of a Meisenheimer complex being the RDS. Computational studies using B3LYP density functional theory have revealed that Mulliken charge density of the electrophilic center decreases as the halogen atom becomes less electronegative. Thus, it has been concluded that the S N Ar reactivity of 6a-6d toward EtOM is governed by electrophilicity of the reaction center but not by nucleofugality of the leaving group. A π-complexed transition-state structure has been proposed to account for the experimental and computational results.

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Metal Ion Catalysis in the Hydrolysis of Esters of 2-Hydroxy-1,10-phenanthroline: The Effects of Metal Ions on Intramolecular Carboxyl Group Participation

Cited by 24 publications

References 36 publications

New Route to Polynuclear Ni(II) and Cu(II) Complexes with Bridging Oxime Groups That Are Inaccessible by Conventional Preparations

New Route to Polynuclear Ni(II) and Cu(II) Complexes with Bridging Oxime Groups That Are Inaccessible by Conventional Preparations

Three‐dimensional structure of xylonolactonase from Caulobacter crescentus: A mononuclear iron enzyme of the 6‐bladed β‐propeller hydrolase family

S_NAr Reactions of 1‐Halo‐2,4‐dinitrobenzenes with Alkali‐Metal Ethoxides: Differential Stabilization of Ground State and Transition State Determines Alkali‐Metal Ion Catalysis or Inhibition

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Metal Ion Catalysis in the Hydrolysis of Esters of 2-Hydroxy-1,10-phenanthroline: The Effects of Metal Ions on Intramolecular Carboxyl Group Participation

Cited by 24 publications

References 36 publications

New Route to Polynuclear Ni(II) and Cu(II) Complexes with Bridging Oxime Groups That Are Inaccessible by Conventional Preparations

New Route to Polynuclear Ni(II) and Cu(II) Complexes with Bridging Oxime Groups That Are Inaccessible by Conventional Preparations

Three‐dimensional structure of xylonolactonase from Caulobacter crescentus: A mononuclear iron enzyme of the 6‐bladed β‐propeller hydrolase family

SNAr Reactions of 1‐Halo‐2,4‐dinitrobenzenes with Alkali‐Metal Ethoxides: Differential Stabilization of Ground State and Transition State Determines Alkali‐Metal Ion Catalysis or Inhibition

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S_NAr Reactions of 1‐Halo‐2,4‐dinitrobenzenes with Alkali‐Metal Ethoxides: Differential Stabilization of Ground State and Transition State Determines Alkali‐Metal Ion Catalysis or Inhibition