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Related Concept Videos

Cooperative Allosteric Transitions01:58

Cooperative Allosteric Transitions

Cooperative allosteric transitions can occur in multimeric proteins, where each subunit of the protein has its own ligand-binding site. When a ligand binds to any of these subunits, it triggers a conformational change that affects the binding sites in the other subunits; this can change the affinity of the other sites for their respective ligands. The ability of the protein to change the shape of its binding site is attributed to the presence of a mix of flexible and stable segments in the...
Cooperative Allosteric Transitions01:58

Cooperative Allosteric Transitions

Cooperative allosteric transitions can occur in multimeric proteins, where each subunit of the protein has its own ligand-binding site. When a ligand binds to any of these subunits, it triggers a conformational change that affects the binding sites in the other subunits; this can change the affinity of the other sites for their respective ligands. The ability of the protein to change the shape of its binding site is attributed to the presence of a mix of flexible and stable segments in the...
Cooperative Allosteric Transitions01:58

Cooperative Allosteric Transitions

Cooperative allosteric transitions can occur in multimeric proteins, where each subunit of the protein has its own ligand-binding site. When a ligand binds to any of these subunits, it triggers a conformational change that affects the binding sites in the other subunits; this can change the affinity of the other sites for their respective ligands. The ability of the protein to change the shape of its binding site is attributed to the presence of a mix of flexible and stable segments in the...
Protein Complex Assembly02:41

Protein Complex Assembly

Proteins can form homomeric complexes with another unit of the same protein or heteromeric complexes with different types.  Most protein complexes self-assemble spontaneously via ordered pathways, while some proteins need assembly factors that guide their proper assembly. Despite the crowded intracellular environment, proteins usually interact with their correct partners and form functional complexes.
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Valence Bond Theory02:42

Valence Bond Theory

Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
Complexation Equilibria: Overview01:23

Complexation Equilibria: Overview

Complexation reactions take place when dative or coordinate covalent bonds form between metal ions and ligands. The compounds formed in these reactions are called coordination compounds. The number of bonds formed between the metal ion and the ligands is called its coordination number. Generally, most metal ions in an aqueous solution are solvated by water molecules and thus exist as aqua complexes.
The equilibrium constant of the complexation reaction is represented as the formation constant...

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Controlling the Size, Shape and Stability of Supramolecular Polymers in Water
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Understanding, controlling and programming cooperativity in self-assembled polynuclear complexes in solution.

Thomas Riis-Johannessen1, Natalia Dalla Favera, Tanya K Todorova

  • 1Department of Inorganic, Analytical and Applied Chemistry, University of Geneva, 30 quai E. Ansermet, 1211 Geneva 4, Switzerland. thomas.riis-johannessen@epfl.ch

Chemistry (Weinheim an Der Bergstrasse, Germany)
|October 22, 2009
PubMed
Summary

Intermetallic interactions in self-assembled polynuclear complexes deviate from simple Coulombic predictions. Solvation and electrostatic repulsion govern these interactions, influencing complex design in solution.

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Area of Science:

  • Coordination Chemistry
  • Supramolecular Chemistry
  • Computational Chemistry

Background:

  • Deviations from statistical binding (cooperativity) in polynuclear complexes arise from intermetallic interactions (DeltaE(M,M)).
  • These interactions in solution are influenced by a balance between electrostatic repulsion and solvation energies.
  • A simple point-charge model predicts significant deviations from Coulomb's law for DeltaE(M,M) in linear polynuclear helicates.

Purpose of the Study:

  • To investigate and quantify the microscopic intermetallic interactions in solution for a series of homometallic and heterometallic polynuclear triple-stranded helicates.
  • To compare experimental findings with predictions from a simple coulombic approach.
  • To understand the influence of metallic charge and intermetallic separation on these interactions for designing new complexes.

Main Methods:

  • Utilized the site binding model to extract ten microscopic interactions defining thermodynamic formation constants.
  • Studied complexes formed from segmental ligands (L1-L11) with Zn(2+) and Lu(3+) cations.
  • Analyzed variations in intermetallic interactions based on cation type (Zn(2+), Lu(3+)) and distance.

Main Results:

  • Apparent intramolecular intermetallic interactions in solution showed non-coulombic behavior.
  • Interactions were more repulsive at longer distances (DeltaE(1-4)(Lu,Lu)>DeltaE(1-2)(Lu,Lu)).
  • Replacing Lu(3+) with Zn(2+) increased interaction magnitude (DeltaE(1-2)(Zn,Lu)>DeltaE(1-2)(Lu,Lu)), and attractive interactions were observed between specific Lu(3+) cations (DeltaE(1-3)(Lu,Lu)<0).

Conclusions:

  • The study demonstrates that intermetallic interactions in solution are complex and do not solely follow Coulomb's law.
  • Solvation and electrostatic factors play a crucial role in determining the nature and magnitude of these interactions.
  • Findings provide insights for the rational design of polynuclear complexes in solution with tailored properties.