NMR and FT-IR Studies on the Association of Derivatives of Thymidine, Adenosine, and 6-N-Methyl-Adenosine in Aprotic Solvents
-
Benjamin Koeppe
Abstract
Associates of 3',5'-O-TBDMS protected derivatives of the 2'-deoxy forms of the nucleosides adenosine, 6-N-methyl-adenosine and thymidine (henceforward simply addressed by their parents' names) and further model systems in dichloromethane and Freon (CDClF2/CDF3) solutions are studied at low temperatures by 1H NMR and FT-IR spectroscopy. N⋯N distances in hydrogen bonds are estimated from chemical shifts of protons in hydrogen bonds employing geometric and spectroscopic hydrogen bond correlations. These distances are in turn employed to derive N–H stretching frequencies from IR spectroscopic hydrogen bond correlations which may be compared to corresponding experimental results. Three isomeric hydrogen bonded dimers of thymidine are characterized in Freon solution at 120 K. Binary associates of thymidine and a series of pyridines are studied; estimated N⋯N distances in the range of 3.08 to 2.85 Å are qualitatively correlated to shifts of N–H stretching bands where in all cases considerable contributions are found in the spectral region below 3000 cm-1. For adenosine, three isomeric binary associates with 4-nitrophenol are found allowing for an assessment of site-specific acceptor capabilities. In associates of thymidine and adenosine, Watson-Crick and Hoogsteen type 1:1 associates (estimated N⋯N distances of 2.85 and 2.90 Å) as well as 2:1 associates bearing only marginally longer H-bonds could be characterized. Two 1:1 associates between thymidine and 6-N-methyl-adenosine are described that are exclusively bonded via N–H⋯N bridges of about 2.97 and 3.08 Å for Watson-Crick and Hoogsteen sites, respectively, which leads to the conclusion that cooperative effects among coupled N–H⋯O and N–H⋯N hydrogen bonds in A-T base pairs are significant as formation of the N–H⋯O bond induces a contraction of around 0.15 Å in the neighboring N–H⋯N bond.
© by Oldenbourg Wissenschaftsverlag, München, Germany
Articles in the same Issue
- Editorial
- Biography of Prof. Dr. Hans-Heinrich Limbach
- Alumni and long term guests of the Limbach group
- NMR and FT-IR Studies on the Association of Derivatives of Thymidine, Adenosine, and 6-N-Methyl-Adenosine in Aprotic Solvents
- Competition between Hydrogen Bonds and Lewis Acid-Base Interactions in the Equilibria between Bis(pentafluorophenyl)borinic Acid and Pyridine: Insights from NMR, Diffractometric and Computational Studies
- Energy Analysis of Competing Non-Covalent Interaction in 1:1 and 1:2 Adducts of Collidine with Benzoic Acids by Means of X-Ray Diffraction
- A TT Dinucleotide with a Nonionic Silyl Backbone: Impact on Conformation and H-Bond Mediated Base Pairing as Studied by Low-Temperature NMR
- Oxygen and Hydrogen Isotopic Preference in Hydration Spheres of Chloride and Sulfate Ions
- Ab Initio Study of Cooperative Effects in Complexes X:HBO:Z, with X, Z=LiH, HNC, HF, HCN, HCl, ClF, and HBO: Structures, Binding Energies, and Spin-Spin Coupling Constants across Intermolecular Bonds
- The Structure and Dynamic Properties of 1H-Pyrazole-4-Carboxylic Acids in the Solid State
- Acridine – a Promising Fluorescence Probe of Non-Covalent Molecular Interactions
- First Example of Hydrogen Bonding to Platinum Hydride
- Interaction of Hydrogen with a Cobalt(0001) Surface
- Immobilization and Characterization of RuCl2(PPh3)3 Mesoporous Silica SBA-3
- Secondary Isotope Effects on 13C and 15N Chemical Shifts of Schiff Bases Revisited
- Analysis of Nutation Patterns in Fourier-Transform NMR of Non-Thermally Polarized Multispin Systems
- The Structure of Supercooled Water and the Mechanism of Homogeneous Nucleation of Ice Ih
- Probing Small Protonated Water Clusters in Acetonitrile Solutions by 1H NMR
- Double Hydrogen Transfer in Low Symmetry Porphycenes
- Nuclear Spin Selective Torsional States: Implications of Molecular Symmetry
Articles in the same Issue
- Editorial
- Biography of Prof. Dr. Hans-Heinrich Limbach
- Alumni and long term guests of the Limbach group
- NMR and FT-IR Studies on the Association of Derivatives of Thymidine, Adenosine, and 6-N-Methyl-Adenosine in Aprotic Solvents
- Competition between Hydrogen Bonds and Lewis Acid-Base Interactions in the Equilibria between Bis(pentafluorophenyl)borinic Acid and Pyridine: Insights from NMR, Diffractometric and Computational Studies
- Energy Analysis of Competing Non-Covalent Interaction in 1:1 and 1:2 Adducts of Collidine with Benzoic Acids by Means of X-Ray Diffraction
- A TT Dinucleotide with a Nonionic Silyl Backbone: Impact on Conformation and H-Bond Mediated Base Pairing as Studied by Low-Temperature NMR
- Oxygen and Hydrogen Isotopic Preference in Hydration Spheres of Chloride and Sulfate Ions
- Ab Initio Study of Cooperative Effects in Complexes X:HBO:Z, with X, Z=LiH, HNC, HF, HCN, HCl, ClF, and HBO: Structures, Binding Energies, and Spin-Spin Coupling Constants across Intermolecular Bonds
- The Structure and Dynamic Properties of 1H-Pyrazole-4-Carboxylic Acids in the Solid State
- Acridine – a Promising Fluorescence Probe of Non-Covalent Molecular Interactions
- First Example of Hydrogen Bonding to Platinum Hydride
- Interaction of Hydrogen with a Cobalt(0001) Surface
- Immobilization and Characterization of RuCl2(PPh3)3 Mesoporous Silica SBA-3
- Secondary Isotope Effects on 13C and 15N Chemical Shifts of Schiff Bases Revisited
- Analysis of Nutation Patterns in Fourier-Transform NMR of Non-Thermally Polarized Multispin Systems
- The Structure of Supercooled Water and the Mechanism of Homogeneous Nucleation of Ice Ih
- Probing Small Protonated Water Clusters in Acetonitrile Solutions by 1H NMR
- Double Hydrogen Transfer in Low Symmetry Porphycenes
- Nuclear Spin Selective Torsional States: Implications of Molecular Symmetry
