Zundel G, Lubos W D, Kölkenbeck K
Biophys J. 1972 Nov;12(11):1509-14. doi: 10.1016/S0006-3495(72)86178-2.
In the double helix formed by the semiprotonated polycytidylic acid (poly C), both strands are linked via NH(+)...N hydrogen bonds. It is a known fact that such symmetrical hydrogen bonds with a double minimum potential well are extremely polarizable. This polarizability causes interaction effects, in particular the proton dispersion forces between such hydrogen bonds. These forces result in a shift of the energy levels and a continuum is observed in the infrared (IR) spectra of solutions in which such hydrogen bonds are present. The continuum occurs in the IR spectrum of the semiprotonated poly C, when the former is present in coiled state. If the double helix forms, an extremely broad band of the NH stretching vibration is observed instead of the continuum, since in the double helix all hydrogen bonds are oriented equally to one another and polarize each other mutually to a strong degree. The proton dispersion forces between the hydrogen bonds balance a considerable part of the electrostatic repulsion of the protons and hence enable the double helix to form. It is conceivable that an unsymmetrical double minimum potential well is present in the NH...N bonds in the DNA and RNA. Such bonds may likewise be considerably more polarizable than electron systems and thus, in this case too, proton dispersion forces would contribute to helix stabilization.
在由半质子化的聚胞苷酸(聚C)形成的双螺旋结构中,两条链通过NH(+)…N氢键相连。一个众所周知的事实是,这种具有双势阱的对称氢键极易极化。这种极化性会引起相互作用效应,特别是这种氢键之间的质子色散力。这些力导致能级发生移动,并且在存在这种氢键的溶液的红外(IR)光谱中会观察到一个连续谱。当半质子化的聚C以卷曲状态存在时,连续谱出现在其红外光谱中。如果形成双螺旋结构,则会观察到NH伸缩振动的极宽带,而不是连续谱,因为在双螺旋结构中所有氢键相互之间的取向相同,并且相互之间有很强的极化作用。氢键之间的质子色散力平衡了质子相当一部分的静电排斥力,从而使双螺旋结构得以形成。可以想象,在DNA和RNA的NH…N键中存在不对称的双势阱。这样的键同样可能比电子系统更具极化性,因此在这种情况下,质子色散力也会有助于螺旋结构的稳定。