NMR进展和二维NMR.pptVIP

(c) DEPT(Distortionless Enhancement by Polarization Transfer) DEPT的优点：对 J 的依赖较小 不同类型化学键的偶合常数变化较大，DEPT谱图的畸变小。 DEPT谱图与去偶的INEPT谱图类似 θ=450 类似于INDEPT τ =1/4J谱图 θ=900 类似于INDEPT τ =2/4J谱图 θ=1350 类似于INDEPT τ =3/4J谱图 13C DEPT900 13C DEPT1350 13C DEPT450 Ethyl Benzene TMS CH3 CH2 CH CH CH CH2 CH3 TMS CH3 θ1+0.79×θ3－1.45 × θ2 CH2 θ1－0.79× θ3 CH θ2 θ1 p －CH3 －C6H4 －C4H9的DEPT谱 (9)核磁共振波谱技术的进展 (a)LC-NMR (b) 反转检测和BIRD脉冲序列 DEPT-1H向非灵敏核(如C13, N15等)极化转移: (c)脉冲场梯度(Pulsed-Field Gradient, PFG) (d) PFG与选择性激发相结合 2)??????????????? 2D NMRSPECTROSCOPY. ?????? (1)脉冲序列 2D NMR: Coupling is the Key 2D detect signals twice (before/after coupling) Same as 1D experiment 90o pulse t1 t2 t1 t2 Transfers between coupled spins 2D NMR Pulse Sequence (2)2D NMR谱的分类： ①二维分解谱 一维是1H 或 13C的化学位移，另一维是1H-1H 或 1H-13C 偶合常数。 ②二维相关谱 (a) 化学位移相关谱（ 1H-1H ， 1H-13C 等） (b) 多量子跃迁谱。 用适当的脉冲序列观测一维谱中不能检测的零量子跃迁和多量子跃迁，在发展期按多量子跃迁频率进动，在混合期变成可检测的横向磁化矢量。 (c) 化学交换/ NOE 二维谱 δ X δA +δ X 2D-INADEQUATE δH ，JHH δH ，JHH Nuclear Overhauser Effect (NOESY ) δ X δA Heteronuclear correlated spectroscopy (HETCOR) δA δA Homoculclear correlated spectroscopy (COSY) δ X JAX Heteronuclear J resolved δ J Homonuclear J resolved f2 f1 ? Information 2-D Experiment (Acronym) 2DJ-NMR Homonuclear 2DJ NMR Heteronuclear 2DJ NMR 2D: Homonuclear COSY： COrrelated SpectroscopY DQF-COSY：(Double Quantum Filtered COSY) Coherence Model RELAY-COSY TOCOSY Total Correlation Spectroscopy (HOHAHA) NOESY： NOE -2D SpectroscopY 2D-Heteronuclear : X-detected HETCOR：HETeronuclear CORrelation COLOC： COrrelation of LOng range Coupling Heteronuclear Proton Relay 1D and 2D INADEQUATE 2D-Heteronuclear : H-detected HMQC：Heteronuclear Multiple Quantum Coherence HSQC： Heteronuclear Single Quantum Coherence HMBC： Heteronuclear Multiple Bond Correlation (3)Homonuclear 2DJ NMR The J-resolved 2D sequence J—Resolved 1H NMR Spectroscopy f1—Spin-Spin Coupling (sw1, 40Hz) f2—1H