Phosphato complexes of cobalt(III). V. The anation of diaquobis(ethylenediamine) cobalt(III) by orthophosphates

1968 ◽  
Vol 21 (7) ◽  
pp. 1745 ◽  
Author(s):  
SF Lincoln ◽  
DR Stranks
Keyword(s):  
Water Exchange ◽  
Ion Pairs ◽  
Kinetic Studies ◽  
Ion Pair ◽  
Significant Shift ◽  
Kcal Mole ◽  
Sharp Maximum ◽  
Anation Reaction ◽  
High Phosphate ◽  
Anation Rate

The anation reaction of [Co en2(OH2)2]3+ by PO43-, and their protonic analogues, is shown to proceed in two kinetic steps. The first is the rapid equilibrium formation of ion-pairs, followed by a slow substitution step. Ion-pair formation causes a significant shift in the cis-trans equilibrium position at pH 7. The anation rate exhibits a sharp maximum around pH 7, and kinetic studies demonstrate that the anation proceeds predominantly via the trans-[Co en2OH.OH2]2+.HPO2-4ion-pair. The rate of inner-sphere substitution from this ion-pair (k = 0.255 min-1 at 47.9�, ΔH? = 30.0 � 0.6 kcal mole-1 =, ΔS? = +(19 � 3) e.u.) is 10-20 times slower than the estimated rate of water exchange with trans-[Co en2OH.OH2I2+. Specific structures are assigned to the ion-pairs and these structures influence rates of substitution. At high phosphate concentrations, there is spectral evidence for the slower formation of diphosphate complexes. The relevance of these kinetic observations to the generation and preparation of phosphato complexes is discussed.

Stereospecific 1,3-H Transfer of Indenols Proceeds via Persistent Ion-Pairs Anchored By NH···Pi Interactions

2018 ◽  
Author(s):  
David Ascough ◽  
Fernanda Duarte ◽  
Robert Paton
Keyword(s):  
Computational Analysis ◽  
Ion Pairs ◽  
Ion Pair ◽  
Hydrogen Atom Transfer ◽  
Polar Solvents ◽  
Chirality Transfer ◽  
Activation Barriers ◽  
Sense And Avoid ◽  
Phase Dynamics ◽  
Pi Interactions

The base-catalyzed rearrangement of arylindenols is a rare example of a suprafacial [1,3]-hydrogen atom transfer. The mechanism has been proposed to proceed via sequential [1,5]-sigmatropic shifts, which occur in a selective sense and avoid an achiral intermediate. A computational analysis using quantum chemistry casts serious doubt on these suggestions: these pathways have enormous activation barriers and in constrast to what is observed experimentally, they overwhelmingly favor a racemic product. Instead we propose that a suprafacial [1,3]-prototopic shift occurs in a two-step deprotonation/reprotonation sequence. This mechanism is favored by 15 kcal mol<sup>-1</sup> over that previously proposed. Most importantly, this is also consistent with stereospecificity since reprotonation occurs rapidly on the same p-face. We have used explicitly-solvated molecular dynamics studies to study the persistence and condensed-phase dynamics of the intermediate ion-pair formed in this reaction. Chirality transfer is the result of a particularly resilient contact ion-pair, held together by electrostatic attraction and a critical NH···p interaction which ensures that this species has an appreciable lifetime even in polar solvents such as DMSO and MeOH.

pH-Dependent Thermal Stability of Vibrio cholerae L-asparaginase

2019 ◽  
Vol 26 (10) ◽  
pp. 743-750 ◽  
Author(s):  
Remya Radha ◽  
Sathyanarayana N. Gummadi
Keyword(s):  
Vibrio Cholerae ◽  
Conformational Changes ◽  
Kinetic Studies ◽  
Structural Features ◽  
Structure Stability ◽  
Kcal Mole ◽  
Scanning Calorimetry ◽  
Wide Range ◽  
Ph Dependent ◽  
Ph Range

Background:pH is one of the decisive macromolecular properties of proteins that significantly affects enzyme structure, stability and reaction rate. Change in pH may protonate or deprotonate the side group of aminoacid residues in the protein, thereby resulting in changes in chemical and structural features. Hence studies on the kinetics of enzyme deactivation by pH are important for assessing the bio-functionality of industrial enzymes. L-asparaginase is one such important enzyme that has potent applications in cancer therapy and food industry.Objective:The objective of the study is to understand and analyze the influence of pH on deactivation and stability of Vibrio cholerae L-asparaginase.Methods:Kinetic studies were conducted to analyze the effect of pH on stability and deactivation of Vibrio cholerae L-asparaginase. Circular Dichroism (CD) and Differential Scanning Calorimetry (DSC) studies have been carried out to understand the pH-dependent conformational changes in the secondary structure of V. cholerae L-asparaginase.Results:The enzyme was found to be least stable at extreme acidic conditions (pH< 4.5) and exhibited a gradual increase in melting temperature from 40 to 81 °C within pH range of 4.0 to 7.0. Thermodynamic properties of protein were estimated and at pH 7.0 the protein exhibited ΔG37of 26.31 kcal mole-1, ΔH of 204.27 kcal mole-1 and ΔS of 574.06 cal mole-1 K-1.Conclusion:The stability and thermodynamic analysis revealed that V. cholerae L-asparaginase was highly stable over a wide range of pH, with the highest stability in the pH range of 5.0–7.0.

scholarly journals Tripodal, Squaramide-Based Ion Pair Receptor for Effective Extraction of Sulfate Salt

Molecules ◽  
2021 ◽  
Vol 26 (9) ◽  
pp. 2751
Author(s):  
Damian Jagleniec ◽  
Marcin Wilczek ◽  
Jan Romański
Keyword(s):  
Ion Pairs ◽  
Binding Mode ◽  
Selective Extraction ◽  
Ion Pair ◽  
Hofmeister Series ◽  
Sulfate Salt ◽  
Lower Affinity ◽  
High Affinity ◽  
Binding Domains ◽  
Hydrated Sulfate

Combining three features—the high affinity of squaramides toward anions, cooperation in ion pair binding and preorganization of the binding domains in the tripodal platform—led to the effective receptor 2. The lack of at least one of these key elements in the structures of reference receptors 3 and 4 caused a lower affinity towards ion pairs. Receptor 2 was found to form an intramolecular network in wet chloroform, which changed into inorganic–organic associates after contact with ions and allowed salts to be extracted from an aqueous to an organic phase. The disparity in the binding mode of 2 with sulfates and with other monovalent anions led to the selective extraction of extremely hydrated sulfate anions in the presence of more lipophilic salts, thus overcoming the Hofmeister series.

Ion pair binding by an l-tyrosine-based polymerizable molecular receptor

2015 ◽  
Vol 39 (8) ◽  
pp. 6216-6222 ◽  
Author(s):  
Szymon Zdanowski ◽  
Jan Romański
Keyword(s):  
Ion Pairs ◽  
Functional Polymers ◽  
Ion Pair

A polymerizable molecular receptor able to bind ion pairs and new functional polymers containing the receptor units were synthesized and characterized.

Axle component separated ion-pair recognition by a neutral heteroditopic [2]rotaxane

2014 ◽  
Vol 50 (13) ◽  
pp. 1540-1542 ◽  
Author(s):  
Richard C. Knighton ◽  
Paul D. Beer
Keyword(s):  
Alkali Metal ◽  
Metal Cation ◽  
Alkali Metal Cation ◽  
Ion Pairs ◽  
Ion Pair ◽  
Sodium Cation ◽  
Halide Anion ◽  
Cooperative Recognition

A neutral heteroditopic pyridine N-oxide axle containing [2]rotaxane, synthesised via sodium cation templation, displays cooperative recognition of alkali metal cation-halide anion ion-pairs in an unprecedented axle component separated ion-pair binding fashion.

Isotope effects and activation parameters for the proton transfer reaction from 1-(4-nitrophenyl)-1-nitroethane to free anions and ion pairs of cesium n-propoxide in n-propanol solvent

1986 ◽  
Vol 64 (6) ◽  
pp. 1021-1025 ◽  
Author(s):  
Arnold Jarczewski ◽  
Grzegorz Schroeder ◽  
Przemyslaw Pruszynski ◽  
Kenneth T. Leffek
Keyword(s):  
Proton Transfer ◽  
Rate Constants ◽  
Isotope Effects ◽  
Ion Pairs ◽  
Activation Parameters ◽  
Solvation Shell ◽  
Ion Pair ◽  
Initial State ◽  
Free Ion ◽  
Deuteron Transfer

Rate constants for the proton and deuteron transfer from 1-(4-nitrophenyl)-1-nitroethane to cesium n-propoxide in n-propanol have been measured under pseudo-first-order conditions with an excess of base for four temperatures between 5 and 35 °C. Using literature values of the fraction of cesium n-propoxide ion pairs that are dissociated into free ions, separate second-order rate constants for the proton and deuteron transfer to the ion pair and to the free ion have been calculated. The cesium n-propoxide ion pair is about 2.8 times more reactive than the free n-propoxide ion. The primary kinetic isotope effects for the two reactions are the same (kH/kD = 6.1–6.3 at 25 °C) within experimental error. The enthalpy of activation is smaller for the ion-pair reaction and the entropy of activation more negative than for the free-ion reaction. For proton transfer, ΔH±ion pair = 8.3 ± 0.2 kcal mol−1, ΔH±ion = 9.6 ± 1.0 kcal mol−1, ΔS±ion pair = −12.3 ± 0.6 cal mol−1 deg−1, ΔS±ion = −10.1 ± 3.4 cal mol−1 deg−1. The greater reactivity of the ion pair relative to the free ion is interpreted in terms of the weaker solvation shell of the ion pair in the initial state.

Octahedral cobalt(III) complexes in dipolar aprotic solvents. II. Association between cis- and trans-dichlorobisethylenediamine cobalt(III) cations,[Co en2 Cl2]+, and chloride and bromide ions in the solvents NN-dimethylformamide, dimethyl sulphoxide, and LVN-dimethylacetamide

1966 ◽  
Vol 19 (1) ◽  
pp. 43 ◽  
Author(s):  
WA Millen ◽  
DW Watts
Keyword(s):  
Spectrophotometric Method ◽  
Ion Pairs ◽  
Ion Association ◽  
Ion Pair ◽  
Association Constants ◽  
Dimethyl Sulphoxide ◽  
Aprotic Solvents ◽  
Ion Association Constants ◽  
Cis And Trans ◽  
Dipolar Aprotic Solvents

Ion association constants at 30� have been determined for the cis-[Co en, Cl2]+Cl- ion pair in NN-dimethylformamide (DMF), NN-dimethylacetamide (DMA), and at 20.0�, 25.0�, and 30.0� in dimethyl sulphoxide (DMSO), by a spectrophotometric method. Association constants for the cis-[Co en2 Cl2]+Br- and the trans- [Co en2 Cl2]+Cl- ion pairs have also been determined in DMF at 30�.

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