Thermodynamic and kinetic data for macrocycle interaction with neutral molecules

Izatt, Reed M.; Bradshaw, Jerald S.; Pawlak, Krystyna; Bruening, Ronald L.; Tarbet, Bryon J.

doi:10.1021/cr00014a005

Cited by 389 publications

(173 citation statements)

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“…Figure 8 shows the frequency of occurrence of binding constants for complexes formed between organic hosts and small neutral organic guests. [29] The binding constants for the 1710 complexes examined are K a = 10 2.2AE1.6 m À1 , which correspond to a binding free energy of À3.1 AE 2.2 kcal mol À1 . The range is similar to that in aqueous solution, but the binding constants are on average about 10-times less.…”

Section: Synthetic Hostsmentioning

confidence: 99%

“…Entropy/ enthalpy compensation is observed also for the 276 cases in which such data have been reported (Figure 10). [29] Figure 6. Examples of non-cyclodextrin water-soluble hosts for organic molecules.…”

Section: Synthetic Hostsmentioning

confidence: 99%

“…Plot of the number of organic host complexes with a particular range of lg K a values in non-aqueous solvents (K a = 10 2.2AE1.6 m À1 ). [29] 2.2. Binding Constants of Proteins 2.2.1.…”

Section: Synthetic Hostsmentioning

confidence: 99%

“…The solvents in which the equilibrium constants were measured are listed. [29] Figure 10. Plot of DH versus DS for organic host-guest complexes in non-aqueous solution; [29] regression analysis gives DH = 229.9(AE 11.0) DSÀ3.2(AE 0.2).…”

Section: Antibody-antigen Complexesmentioning

confidence: 99%

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Binding Affinities of Host–Guest, Protein–Ligand, and Protein–Transition‐State Complexes

et al. 2003

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The affinities of hosts—ranging from small synthetic cavitands to large proteins—for organic molecules are well documented. The average association constants for the binding of organic molecules by cyclodextrins, synthetic hosts, and albumins in water, as well as of catalytic antibodies or enzymes for substrates are 103.5±2.5 M−1. Binding affinities are elevated to 108±2 M−1 for the complexation of transition states and biological antigens by antibodies or inhibitors by enzymes, and to 1016±4 M−1 for transition states with enzymes. The origins of the distributions of association constants observed for the broad range of host–guest systems are explored in this Review, and typical approaches to compute and analyze host–guest binding in solution are discussed. In many classes of complexes a rough correlation is found between the binding affinity and the surface area that is buried upon complexation. Enzymes transcend this effect and achieve transition‐state binding much greater than is expected from the surface areas.

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Section: Synthetic Hostsmentioning

confidence: 99%

Section: Synthetic Hostsmentioning

confidence: 99%

“…Plot of the number of organic host complexes with a particular range of lg K a values in non-aqueous solvents (K a = 10 2.2AE1.6 m À1 ). [29] 2.2. Binding Constants of Proteins 2.2.1.…”

Section: Synthetic Hostsmentioning

confidence: 99%

Section: Antibody-antigen Complexesmentioning

confidence: 99%

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Binding Affinities of Host–Guest, Protein–Ligand, and Protein–Transition‐State Complexes

et al. 2003

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“…3,4 One such structural variation is the replacement of one ether oxygen with nitrogen to give an azacrown ether. 5 Another is the attachment of a functional side arm to the ligand framework to provide the potential for threedimensional complexation of metal ions.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of N-pivot lariat ethers and their metal ion complexation behavior

Bratton¹,

Batsch²

2003

Arkivoc

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Effect of Ring Size on the Complexation and Decomposition of Benzenediazonium Ion in the Presence of Crown Ethers in 1,2-Dichloroethane and the Gas Phase

Kuokkanen

1997

J. Phys. Org. Chem.

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The host-guest complexation and the kinetics of the thermal dediazoniation of benzenediazonium tetrafluoroborate in the presence of unsubstituted and (di)benzene-and dicyclohexane-substituted crown ethers containing 4-10 oxygen atoms were studied by UV spectrophotometry in 1,2-dichloroethane at 40°C. The complexation equilibrium constants K and the stabilizing ability of the complexation (k 2 /k 1 ) were calculated by a kinetic method. Complexation in the gas phase was observed and characterized by fast atom bombardment mass spectrometry (FAB-MS). All complexing agents except 12-crown-4 formed 1:1 complexes [crown ether-PhN 2 ] + under FAB conditions. The complexation caused a hypsochromic shift ⌬ max in the UV spectrum of the benzenediazonium salt, which was largest for hosts containing six oxygen atoms. The thermodynamic and kinetic stability were much greater for insertion-type complexes containing six or more oxygen atoms in the host molecule than for the charge-transfer complexes formed with 15-crown-5. In contrast, 12-crown-4 destabilized benzenediazonium ion owing to the increase in homolytic dediazoniation. 21-Crown-7 was the strongest complexing and stabilizing agent for benzenediazonium ion; with a larger hole size in the host the effects weakened. The effects of benzene and cyclohexane substituents in crown ethers on the thermodynamic and kinetic stability were small compared with the effects of the number of oxygen atoms.

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Thermodynamic and kinetic data for macrocycle interaction with neutral molecules

Cited by 389 publications

References 0 publications

Binding Affinities of Host–Guest, Protein–Ligand, and Protein–Transition‐State Complexes

Binding Affinities of Host–Guest, Protein–Ligand, and Protein–Transition‐State Complexes

Synthesis of N-pivot lariat ethers and their metal ion complexation behavior

Effect of Ring Size on the Complexation and Decomposition of Benzenediazonium Ion in the Presence of Crown Ethers in 1,2-Dichloroethane and the Gas Phase

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