The Influence of Water Content on the 23Na and 31P NMR Spectral Parameters in Solid Na-DNA

Madeddu, Micaela

doi:10.1006/snmr.2002.0062

Cited by 6 publications

(2 citation statements)

References 24 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In recent years solid-state NMR spectroscopy has become a useful tool for direct detection of alkali metal ions in a variety of organic and biological systems. − One important step toward useful applications of this methodology to unknown systems is to establish relationships between NMR spectral parameters of alkali metal ions and ion binding environment. Among cation−ligand interactions, cation−π interactions are of particular importance. − Several years ago, we reported solid-state 23 Na and 39 K NMR spectra for sodium and potassium tetraphenylborates, Na[BPh 4 ] and K[BPh 4 ] .…”

Section: Introductionmentioning

confidence: 99%

A Multinuclear Solid-State NMR Study of Alkali Metal Ions in Tetraphenylborate Salts, M[BPh₄] (M = Na, K, Rb and Cs): What Is the NMR Signature of Cation−π Interactions?

Terskikh

2008

J. Phys. Chem. A

View full text Add to dashboard Cite

We report a multinuclear solid-state ( (23)Na, (39)K, (87)Rb, (133)Cs) NMR study of tetraphenylborate salts, M[BPh 4] (M = Na, K, Rb, Cs). These compounds are isostructural in the solid state with the alkali metal ion surrounded by four phenyl groups resulting in strong cation-pi interactions. From analyses of solid-state NMR spectra obtained under stationary and magic-angle spinning (MAS) conditions at 11.75 and 21.15 T, we have obtained the quadrupole coupling constants, C Q, and the chemical shift tensor parameters for the alkali metal ions in these compounds. We found that the observed quadrupole coupling constant for M (+) in M[BPh 4] is determined by a combination of nuclear quadrupole moment, Sternheimer antishielding factor, and unit cell dimensions. On the basis of a comparison between computed paramagnetic and diamagnetic contributions to the total chemical shielding values for commonly found cation-ligand interactions, we conclude that cation-pi interactions give rise to significantly lower paramagnetic shielding contributions than other cation-ligand interactions. As a result, highly negative chemical shifts are expected to be the NMR signature for cations interacting exclusively with pi systems.

show abstract

Section: Introductionmentioning

confidence: 99%

A Multinuclear Solid-State NMR Study of Alkali Metal Ions in Tetraphenylborate Salts, M[BPh₄] (M = Na, K, Rb and Cs): What Is the NMR Signature of Cation−π Interactions?

Terskikh

2008

J. Phys. Chem. A

View full text Add to dashboard Cite

show abstract

“…These observations are quite similar to those reported previously by Madeddu for CT DNA. [38] The general picture for Na + binding in the CT DNA sample shown in Fig. 1 can be summarized as follows.…”

Section: Resultsmentioning

confidence: 99%

A solid‐state ²³Na NMR study of monovalent cation binding to double‐stranded DNA at low relative humidity

Wong

Yan

Huang

et al. 2008

Magnetic Reson in Chemistry

View full text Add to dashboard Cite

We report a solid-state (23)Na NMR study of monovalent cation (Li(+), Na(+), K(+), Rb(+), Cs(+) and NH(4) (+)) binding to double-stranded calf thymus DNA (CT DNA) at low relative humidity, ca 0-10%. Results from (23)Na--(31)P rotational echo double resonance (REDOR) NMR experiments firmly establish that, at low relative humidity, monovalent cations are directly bound to the phosphate group of CT DNA and are partially dehydrated. On the basis of solid-state (23)Na NMR titration experiments, we obtain quantitative thermodynamic parameters concerning the cation-binding affinity for the phosphate group of CT DNA. The free energy difference (DeltaG degrees ) between M(+) and Na(+) ions is as follows: Li(+) (-1.0 kcal mol(-1)), K(+) (7.2 kcal mol(-1)), NH(4) (+) (1.0 kcal mol(-1)), Rb(+) (4.5 kcal mol(-1)) and Cs(+) (1.5 kcal mol(-1)). These results suggest that, at low relative humidity, the binding affinity of monovalent cations for the phosphate group of CT DNA follows the order: Li(+) > Na(+) > NH(4) (+) > Cs(+) > Rb(+) > K(+). This sequence is drastically different from that observed for CT DNA in solution. This discrepancy is attributed to the different modes of cation binding in dry and wet states of DNA. In the wet state of DNA, cations are fully hydrated. Our results suggest that the free energy balance between direct cation-phosphate contact and dehydration interactions is important. The reported experimental results on relative ion-binding affinity for the DNA backbone may be used for testing theoretical treatment of cation-phosphate interactions in DNA.

show abstract

Quadrupolar Nuclei in Biological Systems

2009

Encyclopedia of Analytical Chemistry

View full text Add to dashboard Cite

Recent advances in solid‐state nuclear magnetic resonance (NMR) methodology and improvement in high‐field NMR instrumentation have generated a new wave of research interests in the application of solid‐state NMR to the study of quadrupolar nuclei in biological systems. These developments now permit increasingly complex biological systems to be probed by direct NMR detection of quadrupolar nuclei. In this article, we describe some recent progress in solid‐state NMR studies of 17 O (S = 5/2), 25 Mg (S = 5/2), 43 Ca (S = 7/2), 67 Zn (S = 5/2), 23 Na (S = 3/2), and 39 K (S = 3/2) nuclei in biological systems with a prognosis for future directions.

show abstract

The Influence of Water Content on the 23Na and 31P NMR Spectral Parameters in Solid Na-DNA

Cited by 6 publications

References 24 publications

A Multinuclear Solid-State NMR Study of Alkali Metal Ions in Tetraphenylborate Salts, M[BPh₄] (M = Na, K, Rb and Cs): What Is the NMR Signature of Cation−π Interactions?

A Multinuclear Solid-State NMR Study of Alkali Metal Ions in Tetraphenylborate Salts, M[BPh₄] (M = Na, K, Rb and Cs): What Is the NMR Signature of Cation−π Interactions?

A solid‐state ²³Na NMR study of monovalent cation binding to double‐stranded DNA at low relative humidity

Quadrupolar Nuclei in Biological Systems

Contact Info

Product

Resources

About

The Influence of Water Content on the 23Na and 31P NMR Spectral Parameters in Solid Na-DNA

Cited by 6 publications

References 24 publications

A Multinuclear Solid-State NMR Study of Alkali Metal Ions in Tetraphenylborate Salts, M[BPh4] (M = Na, K, Rb and Cs): What Is the NMR Signature of Cation−π Interactions?

A Multinuclear Solid-State NMR Study of Alkali Metal Ions in Tetraphenylborate Salts, M[BPh4] (M = Na, K, Rb and Cs): What Is the NMR Signature of Cation−π Interactions?

A solid‐state 23Na NMR study of monovalent cation binding to double‐stranded DNA at low relative humidity

Quadrupolar Nuclei in Biological Systems

Contact Info

Product

Resources

About

A Multinuclear Solid-State NMR Study of Alkali Metal Ions in Tetraphenylborate Salts, M[BPh₄] (M = Na, K, Rb and Cs): What Is the NMR Signature of Cation−π Interactions?

A Multinuclear Solid-State NMR Study of Alkali Metal Ions in Tetraphenylborate Salts, M[BPh₄] (M = Na, K, Rb and Cs): What Is the NMR Signature of Cation−π Interactions?

A solid‐state ²³Na NMR study of monovalent cation binding to double‐stranded DNA at low relative humidity