Temperature Dependent Self-Diffusion Coefficients of Valinomycin and the Potassium-Valinomycin Complex

Convection effect in liquids has been one of the main targets to be overcome in pulsed-field-gradient NMR measurements of self-diffusion coefficients since the temperature gradient along the sample tube generated by the heating and/or cooling process causes the effect, resulting in additional diffusion. It is known that the capillary is the most appropriate tube type for diffusion experiments at variable temperatures since the narrower tube suppresses convection effectively. For evaluating the properties of hydrogen bonding, diffusion coefficients of the -complexed and free valinomycin in a micro tube have been determined at various temperatures. From the analysis of the obtained diffusion coefficient values, we could conclude that the intramolecular hydrogen bonding in both of the complexed and free valinomycin in a non-polar solvent is preserved over the observed temperature range, and the temperature dependence of hydrogen bonding is more pronounced in free valinomycin. It is also thought that there is no big change in the radius of the -complexed as temperature is varied, and the ratio of overall radius, is slightly decreased as temperature rises.

[1]  D. Urry,et al.  Temperature dependence of amide proton chemical shifts: the secondary structures of gramicidin S and valinomycin. , 1969, Biochemical and biophysical research communications.

[2]  D. Urry,et al.  Solution Conformation of Valinomycin-Potassium Ion Complex , 1970, Science.

[3]  H. Hauptman,et al.  Valinomycin Crystal Structure Determination by Direct Methods , 1972, Science.

[4]  Warren J. Goux,et al.  The impact of Rayleigh-Benard convection on NMR pulsed-field-gradient diffusion measurements , 1990 .

[5]  Anders Hult,et al.  Synthesis, Characterization, and 1H NMR Self-Diffusion Studies of Dendritic Aliphatic Polyesters Based on 2,2-Bis(hydroxymethyl)propionic Acid and 1,1,1-Tris(hydroxyphenyl)ethane , 1996 .

[6]  M. Shapiro,et al.  Mixture Analysis in Combinatorial Chemistry. Application of Diffusion-Resolved NMR Spectroscopy. , 1996, The Journal of organic chemistry.

[7]  P. Ingman,et al.  Effects of Thermal Convection on NMR and Their Elimination by Sample Rotation , 1996 .

[8]  Furó,et al.  Temperature imaging by 1H NMR and suppression of convection in NMR probes , 1998, Journal of magnetic resonance.

[9]  Charles S. Johnson Diffusion Ordered Nuclear Magnetic Resonance Spectroscopy: Principles and Applications , 1999 .

[10]  J. Keeler,et al.  Measurement of convection and temperature profiles in liquid samples. , 1999, Journal of magnetic resonance.

[11]  Alexej Jerschow Thermal convection currents in NMR: flow profiles and implications for coherence pathway selection , 2000, Journal of magnetic resonance.

[12]  S. Berger,et al.  The qualitative probing of hydrogen bond strength by diffusion-ordered NMR spectroscopy , 2000 .

[13]  Y. Cohen,et al.  Spontaneous formation of hexameric resorcinarene capsule in chloroform solution as detected by diffusion NMR. , 2002, Journal of the American Chemical Society.

[14]  G. Lindblom,et al.  Encapsulation and Diffusion of Water-Soluble Dendrimers in a Bicontinuous Cubic Phase , 2002 .

[15]  Y. Cohen,et al.  Effect of a cationic guest on the characteristics of the molecular capsule of resorcinarene: a diffusion NMR study. , 2003, Organic letters.

[16]  P. Pregosin,et al.  Low temperature 1H-, 19F-, and 31P-PGSE diffusion measurements. Applications to cationic alcohol complexes , 2003 .

[17]  W. Price,et al.  A new type of sample tube for reducing convection effects in PGSE-NMR measurements of self-diffusion coefficients of liquid samples. , 2004, Journal of magnetic resonance.