Thermodynamic Studies on the Recognition of Flexible Peptides by Transition-Metal Complexes

Sun, Shuguang; Fazal, Md. Abul; Roy, B. C.; Chandra, Binita; Mallik, Sanku

doi:10.1021/ic0108742

Cited by 15 publications

(6 citation statements)

References 34 publications

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“…However, the enthalpic advantage for the complexation with ( S , S )- 11 (ΔΔ H = −2.6 kcal/mol) is canceled by the less negative − T Δ S (Δ(− T Δ S ) = 2.1 kcal/mol), which results in a similar log K app1 value (Δ G value) for complexation to that with ( R , R )- 11 . These results suggest that this complexation system obeys the empirical rule of enthalpy−entropy compensation. , …”

Section: Resultsmentioning

confidence: 99%

Molecular Recognition of Inositol 1,4,5-Trisphosphate and Model Compounds in Aqueous Solution by Ditopic Zn²⁺ Complexes Containing Chiral Linkers

et al. 2010

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We report on molecular recognition of inositol 1,4,5-trisphosphate (Ins(1,4,5)P(3)), an important intracellular second messenger, and some related model compounds, cyclohexanediol bisphosphate derivatives (CDP(2)), by ditopic Zn(2+) complexes containing chiral linkers ((S,S)- and (R,R)-11) in aqueous solution at physiological pH. A crystal structure analysis of (S,S)-11 indicated that the distance between two Zn(2+) ions (6.8 A) is suitable for accommodating two phosphate groups at the 4- and 5-positions of Ins(1,4,5)P(3) and two phosphate groups of trans-1,2-CDP(2). (1)H NMR, (31)P NMR, potentiometric pH, and isothermal calorimetric titration data indicate that (S,S)-11 forms 1:1 complexes with (S,S)- and (R,R)-1,2-CDP(2) at pH 7.4 and 25 degrees C. The apparent 1:1 complexation constants (log K(app)) for (S,S)-11-(S,S)-1,2-CDP(2) and (S,S)-11-(R,R)-1,2-CDP(2) (K(app) = [(S,S)-11-1,2-CDP(2) complex]/[(S,S)-11][1,2-CDP(2)] (M(-1))) were determined to be 7.6 +/- 0.1 and 7.3 +/- 0.1, respectively, demonstrating that both enantiomers of 11 bind to chiral trans-1,2-CDP(2) to almost the same extent. The log K(app) value of 6.3 was obtained for a 1:1 complex of (S,S)-11 with cis-1,3-CDP(2), while a small amount of 2:1 (S,S)-11-cis-1,3-CDP(2) was detected, as evidenced by electrospray ionization mass spectrometry (ESI-MS). In contrast, 11 formed several complexes with trans-1,4-CDP(2). On the basis of isothermal titration calorimetry data for (S,S)- and (R,R)-11 with Ins(1,4,5)P(3), it was concluded that 11 forms a 2:1 complex with Ins(1,4,5)P(3), in which the first molecule of 11 binds to the 4- and 5-phosphates of Ins(1,4,5)P(3) and the second molecule of 11 binds to the 1- and 5-phosphates.

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Section: Resultsmentioning

confidence: 99%

Molecular Recognition of Inositol 1,4,5-Trisphosphate and Model Compounds in Aqueous Solution by Ditopic Zn²⁺ Complexes Containing Chiral Linkers

et al. 2010

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“…This effect can be seen in receptors 7 – 9 , as the binding sites of the receptors change from three guanidinium groups to two boronic acids and one guanidinium group. The slope of the EEC graph was determined to be 0.8, which means that the free energy of binding is more sensitive to changes in entropy 54. A slope of less than one suggests that in the rational design of a receptor to bind with better binding contacts to the host, the increased exothermicity of binding (Δ H 0 ) would be defeated by the compensating entropy ( T Δ S 0 )…”

Section: Resultsmentioning

confidence: 99%

Thermodynamic Analysis of Receptors Based on Guanidinium/Boronic Acid Groups for the Complexation of Carboxylates, α‐Hydroxycarboxylates, and Diols: Driving Force for Binding and Cooperativity

Wiskur

Lavigne

Metzger

et al. 2004

Chemistry A European J

139

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The thermodynamics of guanidinium and boronic acid interactions with carboxylates, alpha-hydroxycarboxylates, and diols were studied by determination of the binding constants of a variety of different guests to four different hosts (7-10). Each host contains a different combination of guanidinium groups and boronic acids. The guests included molecules with carboxylate and/or diol moieties, such as citrate, tartrate, and fructose, among others. The Gibbs free energies of binding were determined by UV/Vis absorption spectroscopy, by use of indicator displacement assays. The receptor based on three guanidinium groups (7) was selective for the tricarboxylate guest. The receptors that incorporated boronic acids (8-10) had higher affinities for guests that included alpha-hydroxycarboxylate and catechol moieties over guests containing only carboxylates or alkanediols. Isothermal titration calorimetry revealed the enthalpic and entropic contributions to the Gibbs free energies of binding. The binding of citrate and tartrate was investigated with hosts 7-10, for which all the binding events were exothermic, with positive entropy. Because of the selectivity of hosts 8-10, a simple boronic acid (14) was also investigated and determined to be selective for alpha-hydroxycarboxylates and catechols over amino acids and alkanediols. Further, the cooperativity of 8 and 9 in binding tartrate was also investigated, revealing little or no cooperativity with 8, but negative cooperativity with 9. A linear entropy/enthalpy compensation relationship for all the hosts 7-10, 14, and the carboxylate-/diol-containing guests was also obtained. This relationship indicates that increasing enthalpy of binding is offset by similar losses in entropy for molecular recognition involving guanidinium and boronic acid groups.

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“…From the data, a binding model with a three-point contact of the protein-affinity tags to the Cu(II)−IMAC column at pH 7 was derived (Figure ). Since 2000, the group of Mallik reported IDA metal complexes capable of binding strongly to histidine patterns of flexible peptides in water . To achieve strong and selective binding, the geometry of the IDA complex and the target histidine pattern need to be complementary.…”

Section: 2 Recognition Processes In Solution321 Peptide and Protein B...mentioning

confidence: 99%

Reversible Coordinative Bonds in Molecular Recognition

2006

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Thermodynamic Studies on the Recognition of Flexible Peptides by Transition-Metal Complexes

Cited by 15 publications

References 34 publications

Molecular Recognition of Inositol 1,4,5-Trisphosphate and Model Compounds in Aqueous Solution by Ditopic Zn²⁺ Complexes Containing Chiral Linkers

Molecular Recognition of Inositol 1,4,5-Trisphosphate and Model Compounds in Aqueous Solution by Ditopic Zn²⁺ Complexes Containing Chiral Linkers

Thermodynamic Analysis of Receptors Based on Guanidinium/Boronic Acid Groups for the Complexation of Carboxylates, α‐Hydroxycarboxylates, and Diols: Driving Force for Binding and Cooperativity

Reversible Coordinative Bonds in Molecular Recognition

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Thermodynamic Studies on the Recognition of Flexible Peptides by Transition-Metal Complexes

Cited by 15 publications

References 34 publications

Molecular Recognition of Inositol 1,4,5-Trisphosphate and Model Compounds in Aqueous Solution by Ditopic Zn2+ Complexes Containing Chiral Linkers

Molecular Recognition of Inositol 1,4,5-Trisphosphate and Model Compounds in Aqueous Solution by Ditopic Zn2+ Complexes Containing Chiral Linkers

Thermodynamic Analysis of Receptors Based on Guanidinium/Boronic Acid Groups for the Complexation of Carboxylates, α‐Hydroxycarboxylates, and Diols: Driving Force for Binding and Cooperativity

Reversible Coordinative Bonds in Molecular Recognition

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Molecular Recognition of Inositol 1,4,5-Trisphosphate and Model Compounds in Aqueous Solution by Ditopic Zn²⁺ Complexes Containing Chiral Linkers

Molecular Recognition of Inositol 1,4,5-Trisphosphate and Model Compounds in Aqueous Solution by Ditopic Zn²⁺ Complexes Containing Chiral Linkers