Nuclear Magnetic Resonance hn 1938 Bloch and Parcell in 1946.Through the 1960sC NMR aktreprent72n 者名化学家、诺贝尔奖金获得者库愿指导下进行票红素化学 的研究。 Nuclear Magnetic Resonance Introduction Spectroscopy is the cornerstone of the econd half of the ules.NMR studies are mov Using spectroscopic techniques to solve n has bee structural problems. 。 Brief History of NMR 上这技术已成为常规方法了，这些技术已成为天然产 1945 Detection of NMR sigals 才完成了结构确定，用了150年时间，番木重装 -Sp 30M 1952 Bloch&Purcell Recsived the First 的主方法法化.而今天确定 个比杂的天 Nobel Prize(Stanford&Harvard) 1953 Overhauser Effect 2 2 7 1935年汪猷赴德国慕尼黑大学化学研究所，在著名化学 家、诺贝尔奖获得者维兰德指导下当研究生。1937年冬，汪 猷获慕尼黑大学最优科学博士学位。1938年秋，他又去海德 堡威廉皇家科学院医学研究院化学研究所任客籍研究员，在 著名化学家、诺贝尔奖金获得者库恩指导下进行藏红素化学 的研究。 Heinrich Otto Wieland 1927 汪 猷 Richard Kuhn 1938 1900.12.3-1967.8.1 8 NMR spectroscopy was developed in the late 1950s following the discovery of nuclear magnetic resonance by Bloch and Purcell in 1946. Through the 1960s 13C NMR became increasingly important and from 1972 was aided by a method known as the Fourier-transform technique. Another variation known as CIDNP (chemically induced dynamic nuclear polarization) appeared in about 1972 and was a valuable probe for free radical reactions of all kinds. Nuclear Magnetic Resonance 9 Through the 1970s NMR was successfully applied to a vast range of problems in conformational analysis, and in due course extended to biological molecules. The coming of 3D NMR in the late 1980s made these studies much more practical for structural analysis of proteins, nucleic acids and other complex molecules. NMR studies are now so ubiquitous that it is hard to imagine chemistry without them. Their impact on structure determination has been immense. Nuclear Magnetic Resonance 10 Introduction Spectroscopy is the cornerstone of the organic chemistry of the second half of the twentieth century. Using spectroscopic techniques to solve structural problems. 11 十几年前像HMBC、TOCSY等2DNMR等技术还是波谱 学家刚开发的脉冲序列，可是在近几年市售的NMR波谱仪 器上这些技术已成为常规方法了，这些技术已成为天然产 物结构测定的强有力的工具。众所周知的吗啡(morphine) 是1803年由Serturner分离得到的，直到1952年全合成成功 才完成了结构确定，用了150年时间，番木鳖碱 (Strychnine，士的宁)的结构确定用了半个多世纪(1891- 1946)，耗费了几代杰出化学家的心血，原因是当时确定结 构的主要方法是湿法化学。而今天确定一个比较复杂的天 然化合物的结构已变成研究生的科研训练课程，一般只需 几个小时、几天、几周或几个月即可完成。 12 Brief History of NMR • 1945 Detection of NMR signals • 1949 Proctor et al Discovery of Chemical Shift • 1951 Hahn et al Discovery of Spin-Spin Coupling • 1952 First NMR Spectrometer (Varian 30 MHz) • 1952 Bloch & Purcell Received the First Nobel Prize (Stanford & Harvard) • 1953 Overhauser Effect • 1959 Vicinal J Dependence on Dihedral Angle (Karplus 1963) Bloch et al. at Stanford Purcell et al. at Harvard Ethanol J. Am. Chem. Soc., 85, 2870 (1963)