Proni G, Gottarelli G, Mariani P, Spada G P
Dipartimento di Chimica Organica A. Mangini, Università di Bologna, Italy.
Chemistry. 2000 Sep 1;6(17):3249-53. doi: 10.1002/1521-3765(20000901)6:17<3249::aid-chem3249>3.0.co;2-f.
While the handedness of the cholesteric phases formed by assembled guanosine derivatives (G-wires) follow the correlation right-handed helices-->right-handed cholesterics (left-handed -->left-handed), the cholesteric phase formed by B-DNA (right-handed helix) is left-handed. This apparent discrepancy is overcome by considering pitch (p) variations with temperature. Plots of p(-1) versus T(-1) have, in fact, the same trend (positive intercept and negative slope) in the case of right-handed G-wires and B-DNA, while for the left-handed G-wire of deoxyguanosine monophosphate (dGMP), the opposite behavior is observed (negative intercept and positive slope). Therefore, the relation between molecular handedness and cholesteric helicity cannot, in general, be assessed by using measurements based on a single temperature; hence the temperature variation of the cholesteric parameters should be investigated. In all cases there is no remarkable salt effect on the cholesteric parameters.
虽然由组装的鸟苷衍生物(G-线)形成的胆甾相的旋光性遵循右手螺旋→右手胆甾相(左手→左手)的相关性,但由B-DNA(右手螺旋)形成的胆甾相是左手的。通过考虑螺距(p)随温度的变化,这种明显的差异得以克服。实际上,在右手G-线和B-DNA的情况下,p(-1)对T(-1)的图具有相同的趋势(正截距和负斜率),而对于脱氧鸟苷单磷酸(dGMP)的左手G-线,则观察到相反的行为(负截距和正斜率)。因此,一般不能通过基于单一温度的测量来评估分子旋光性与胆甾螺旋性之间的关系;因此,应该研究胆甾参数的温度变化。在所有情况下,盐对胆甾参数没有显著影响。