核磁共振(NMR)波譜學(xué)原理及其應(yīng)用

1、Data processingrf consoleTransmitterReceiverMagnetSample tubeProbe 020406080100120140PPMrf pulseB0Sample tubeinside coil FTSpectrumFIDpeakE0 B0nodetroughEBt0 if abscissa scale is time if abscissa scale is lengthElectromagnetic wave with electric vector E and magnetic vector B 1to B0m=+m=-半整數(shù)214P B0m

2、=+m=-PZ=PZ=-m=+1m=0m=-1PZ=PZ=0PZ=-m=+ ( )m=- ( )z, BO 自旋為自旋為的核在磁場(chǎng)中的兩個(gè)進(jìn)動(dòng)錐體的核在磁場(chǎng)中的兩個(gè)進(jìn)動(dòng)錐體 2B0m=- ( )E =+ B0m=-1m=+ ( )E =- B0m=+1E-1= B0m=0E+1=- B0E0=0E0I=1H, 13CI=12H, 14N E E2EB0B1B2m=+ ( )m=- ( )0N N =e- E/K T 1- EK T1-=K T B0N (m=- )N (m=+ )=exp EKT=exp1.66x10-25J1.38x10-23JK-1 298K=0.99996z, BO m=

3、+m=-N N M0E-=+ B0E+=- B0EBB00 E= 1質(zhì)子在靜磁場(chǎng)中的能級(jí)差質(zhì)子在靜磁場(chǎng)中的能級(jí)差 2BEB00m=-1m=+1m=0E-1= B0E0=0E+1=- B014N(I=1)在靜磁場(chǎng)中的能級(jí)差在靜磁場(chǎng)中的能級(jí)差tpf1f單個(gè)射頻的脈沖單個(gè)射頻的脈沖脈沖脈沖核自旋系數(shù)FT激勵(lì)響應(yīng)FID波譜脈沖激勵(lì)的系統(tǒng)脈沖激勵(lì)的系統(tǒng) 2 2B測(cè)-B標(biāo)B標(biāo)x106SiCH3H3CCH3CH3SiCH3H3CCH3SO3-Na+TMSDDS9876543210ppm0.0000.9280.9460.9651.3751.3941.9021.9211.9404.0264.3144.3324.

4、3507.6477.7048.8774.2519.7213.2314.100.5032.5710.305.33H1 solvent:aectone C4mimPF6 2004.12.13 T1X=0.05 good140130120110100908070605040302010ppm13.6119.9129.4929.6829.8730.0630.2632.6436.5350.20123.33124.70137.31C13 solvent:aectone C4mimPF6 2004.12.13 T1X=0.05電負(fù)性遞增去屏蔽遞增5.59OO6.488.05OOMeOOHMeO6.607.9

5、57.05O4.436.61HHx+苯環(huán)的屏蔽作用十八輪烯烯質(zhì)子:7.97.0HHHHHHHHHHHHHHHHHH9.28-2.9HHHH-1.20.90.9CO+CC+雙鍵的磁各向異性CCRH+叁鍵a和單鍵b的磁各向異性abCC+HHHH+單鍵的磁各向異性對(duì)直立和平伏氫的影響H3CO H3 .3 43 .3 7H3CCHCH3OH1.133.903.20H2COHH3C1.163.594.00H3CH2CCOCH32.062.391.02H2CCCH3CHOCH3H2CCN2.291.761.125.16BrH2CClH2COCH3H2CCN2.643.623.46FCHFCOOH7.406

6、.10一些sp3雜環(huán)碳上氫核的化學(xué)位移0.221.961.511.441.541.78O1.65O3.031.96O2.062.02O2.221.81.8O2.38O2.301.941.521.52一些環(huán)狀化合物sp3雜環(huán)碳上氫核的化學(xué)位移HH3CCO2CH3CH36.731.73H3CHCO2CH3CH31.975.98一些烯氫的化學(xué)位移1.651.965.595.805.902.157.267.667.308.317.917.39N7.647.258.50NN7.509.24NN8.777.379.26NH6.307.176.98CHO9.4511.0一些芳環(huán)和芳雜環(huán)氫的化學(xué)位移CCHH1

7、.80CCHR1.73-1.88CCHAr2.71-3.37CCHCO2H2.23CCHC1.95CR一些炔氫的化學(xué)位移一些氫鍵質(zhì)子的化學(xué)位移范圍一些氫鍵質(zhì)子的化學(xué)位移范圍0123PPM1H13C195HzV195HzV1H13CHHHHHH CCCCCCV1H-13C標(biāo)量偶合對(duì)1H的能級(jí)和譜線的影響JJVAAXAJ/4J/4J/4J/4XAXAXAAXAXAVAVAVXVXAAXXVV(a)(b)(c)自旋自旋A和X能級(jí)圖和波譜(a)核與磁場(chǎng)0的相互作用(b) X核與磁場(chǎng)0的相互作用(c) 標(biāo)量偶合 J=JAX0JA XJA XJA MMMXXXXMMSpin-spin coupling i

8、n an AMX spin systemJA XJA XJA X(3) 與二個(gè)等性核()AX2的偶合JA XJA XJA X(4) 與三個(gè)等性核()AX3的偶合Spin-spin coupling in an AX3 spin system1111211331146411510105116152015610123-1-2-3AA XA X2A X3A X4A X5A X6(V -VA)/JA X(5) 與n個(gè)等性核()AXn的偶合VAVAVXVXVX-1+10(a)(b)(c)(6)核的偶合例1:14NH(I=1)HBHBHHHHbridge protons300MHz500MHztermin

9、al protons例2:11B(I=3/2)CCHHFFCHHFFHHHHHHHHOOHHHH0.8HzHOH0.4HzCCCH3CH3CHH3.0HzH2CCCHCH2CH32.6HzXHHHX=O, HNup to 0.7HzHH3CHHHHHHHHHH123456 烷烴的13C化學(xué)位移 丙烷衍生物的丙烷衍生物的13C化學(xué)位移化學(xué)位移 環(huán)烷烴的環(huán)烷烴的13C化學(xué)位移化學(xué)位移 直鏈烯烴的直鏈烯烴的13C化學(xué)位移化學(xué)位移 單取代乙烯的單取代乙烯的13C化學(xué)位移化學(xué)位移 128.5127.7125.6133.3126.2128.1125.3131.8126.6128.3126.3126.3122.4131.9130.119.6136.4129.9126.116.9132.3單取代基苯環(huán)的單取代基苯環(huán)的13C化學(xué)位移化學(xué)位移 CCCHHHH212.673.5 醛和酮的醛和酮的13C化學(xué)位移化學(xué)位移 醋酸衍生物的醋酸衍生物的13C化學(xué)位移化學(xué)位移 取代醋酸的取代醋酸的13C化學(xué)位移化學(xué)位移 90 x90 xbroadbanddecouplingv1(13C)v2