DNA’s Chiral Spine of Hydration
نویسندگان
چکیده
The iconic helical structure of DNA is stabilized by the solvation environment, where a change in the hydration state can lead to dramatic changes to the DNA structure. X-ray diffraction experiments at cryogenic temperatures have shown crystallographic water molecules in the minor groove of DNA, which has led to the notion of a spine of hydration of DNA. Here, chiral nonlinear vibrational spectroscopy of two DNA sequences shows that not only do such structural water molecules exist in solution at ambient conditions but that they form a chiral superstructure: a chiral spine of hydration. This is the first observation of a chiral water superstructure templated by a biomolecule. While the biological relevance of a chiral spine of hydration is unknown, the method provides a direct way to interrogate the properties of the hydration environment of DNA and water in biological settings without the use of labels.
منابع مشابه
The H2O Helix: The Chiral Water Superstructure Surrounding DNA
The double helix structure of DNA comes as close as it gets in science to a household brand. Results reported by Petersen and co-workers uncover a new structure buried just at the surface of DNA: a chiral, helical superstructure of water molecules (Figure 1). The authors applied second-order nonlinear optical spectroscopy to observe the collective orientation of these waters. They propose that ...
متن کاملThe Clusters-in-a-Liquid Approach for Solvation: New Insights from the Conformer Specific Gas Phase Spectroscopy and Vibrational Optical Activity Spectroscopy
Vibrational optical activity spectroscopies, namely vibrational circular dichroism (VCD) and Raman optical activity (ROA), have been emerged in the past decade as powerful spectroscopic tools for stereochemical information of a wide range of chiral compounds in solution directly. More recently, their applications in unveiling solvent effects, especially those associated with water solvent, have...
متن کاملKinetics of DNA hydration.
The hydration of the d(CGCGAATTCGCG) B-DNA duplex in solution was studied by nuclear magnetic relaxation dispersion (NMRD) of the water nuclei 1H, 2H, and 17O, and by nuclear Overhauser effects (NOEs) in high-resolution two-dimensional 1H NMR spectra. By comparing results from the free duplex with those from its complex with netropsin, water molecules in the "spine of hydration" in the AATT reg...
متن کاملRegularities in formation of the spine of hydration in the DNA minor groove and its influence on the DNA structure.
Computer calculations as well as an analysis of space-filling models and literature data allowed the following conclusions to be made: an ordered spine of water in the DNA minor groove, similar to that revealed in the CGCGAATTCGCG crystal, seems to exist in DNA crystals, fibers and solutions; it is shown that this spine may be formed on A/T runs containing no TA step while on the TA step the sp...
متن کاملNMR observation of individual molecules of hydration water bound to DNA duplexes: direct evidence for a spine of hydration water present in aqueous solution.
The residence times of individual hydration water molecules in the major and minor grooves of DNA were measured by nuclear magnetic resonance (NMR) spectroscopy in aqueous solutions of d-(CGCGAATTCGCG)2 and d-(AAAAATTTTT)2. The experimental observations were nuclear Overhauser effects (NOE) between water protons and the protons of the DNA. The positive sign of NOEs with the thymine methyl group...
متن کامل