现代分析技术与应用：第十四章 核磁共振波谱技术 (2).ppt

Boltzmann 分布：低能态自旋数与高能态自旋数 N+/ N- = e -?E/KT ? 1 + ?E/KT =1+ ?·h H0 /2?KT ? 1.000009，非常小。 H0=1.41TG ? = 26.752 (107 rad./s.T) K——Boltzmann常数，1.3805x10-23 J/K T——绝对温度 h ——普朗克常数 6.624 ? 10-34 J S 易跃迁饱和 N+= N-(不能以辐射的形式释放能量） 灵敏度正比N+/ N， 基态与激发态之间的能级差小，灵敏度较其他波谱技术小 能级差不是一个常数，同一核素，H0 强度增加，跃迁频率?增加 1H Υ = 26.752 (107 rad./s.T) H0 = 4.7 T， 200 MHz H0 = 7.05 T，300 MHz ωi = ?iHo (1- σ) 周期表中几乎所有元素都有能产生核磁共振吸收的同位素 I ? 0原子核， ? ? 0，都有核磁共振现象 常用于NMR 核素： 1H 、13C、 15N、19F、31P I=1/2，核电荷分布均匀，电四极矩eQ = 0,核磁共振的谱线窄　 = 2??0 = ? H0 ? ＝ ? P = ? h/2?[ I ( I + 1)]1/2 不同的核素γ不同，同一磁场强度下? 不同 当H0 =4.7 T时： 1H Υ = 26.752 (107 rad./s.T) 200 MHz 13C Υ = 6.728 (107 rad./s.T) 50.3 MHz 19F Υ = 25.181 (107 rad./s.T) 188.2 MHz 31P Υ = 10.841 (107 rad./s.T) 81　 MHz = 2??0 = ? H0 ?H = 26.752 (107 rad./s.T) * 4.7 T / （2?）= 200 MHz Properties of Nuclei Most Useful for Biological Studies 不同核素灵敏度不同 N+/ N- = e -?E/KT 激发射频与无线电波对应（基态和激发态之间能级差很小） 　 1H Υ = 26.752 (107 rad./s.T)，H0 = 4.7 T， λ＝1.5（ m） 　　 = 2??0 = ? H0 λ= C/ ? C——光速 = 299 792 458 m / s = 2??0 = ? H0 ?H = 26.752 (107 rad./s.T) * 4.7 T / （2?）= 200 MHz 驰豫(Relaxation ) 核自旋系统，通过自旋和晶格之间的相互作用，以及自旋之间的相互作用，逐步由非平衡态又恢复到平衡态重建Boltzmann分布的过程叫驰豫。驰豫过程的快慢用驰豫时间Ｔ来描写． ?2. NMR lines are extraordinarily sharp, and extraordinarily close together (in energetic terms) compared to higher energy spectroscopic methods. So much so that Heisenberg uncertainty broadening (which is a function of lifetime of a given energy state, and hence relaxation rates) is a dominant feature of many NMR spectra, and can limit our ability to measure and interpret spectra. When relaxation is very fast, NMR lines are broad,?J-coupling may not be resolved or the signal may even be difficult or impossible to detect. ??3. The success of many multipulse experiments, especially 2D and 3D spectra, depends crucially on proper consideration of relaxation times. ?2. NMR lines are extraordinarily sharp, and