スペクトル編集

J変調スピンエコー （SFT, APT）
Refocused HSQC
DEPT/DEPTQ/PENDANT

refocused HSQCによる編集
CHn系のrefocused (full INEPT) HSQC
13Cの信号強度 ∝ (γH/γC)

5/2 n sin π1Jn-1 π1J tCHt cos
CH

信号強度は1Hの数にほぼ比例する。
13Cの信号が最大になる時間は1Hの数に依存する。

n=1では t=1/2J で最大値 1×γH/γC

t=1/2JのときCH ∝ 1n=2では t=1/4J で最大値 2×γH/γC

CH2 ∝ 0n=3では t={cos-1√(2/3)}/(πJ) で最大値 (2/√3)×γH/γC

CH3 ∝ 0CH ∝ sinπJt
CH2 ∝ 2 sinπJt cosπJt
CH3 ∝ 3 sinπJt cos2πJt

DEPTによる編集
β = 45° DEPT-45CH ∝ 1/√2 ≈ 0.71

βyI
1/2JIS1/2JIS1/2JISSσ1 σ2σ3 σ4σ5CH ∝ sinβCH2 ∝ 2 sinβ cosβCH3 ∝ 3 sinβ cos2β

CH2 ∝ 2 × 1/√2 × 1/√2 = 1CH3 ∝ 3 × 1/√2 × (1/√2)2 ≈ 1.06
β = 90° DEPT-90
CH ∝ 1CH2 ∝ 2 × 1 × 0 = 0CH3 ∝ 3 × 1 × 0 = 0β = 135° DEPT-135CH ∝ 1/√2 ≈ 0.71
CH2 ∝ 2 × 1/√2 × (-1/√2) = -1CH3 ∝ 3 × 1/√2 × (-1/√2)2 ≈ 1.06

CHのDEPTβyI1/2JIS

1/2JIS

1/2JIS

S
σ1 σ2

σ3 σ4

σ5

Q1. ISスピン系において、σ1でのプロダクトオペレータを表示せよ。
Q2. ISスピン系において、σ2でのプロダクトオペレータを表示せよ。
Q3. ISスピン系において、σ3でのプロダクトオペレータを表示せよ。
Q4. ISスピン系において、σ4でのプロダクトオペレータを表示せよ。
Q5. ISスピン系において、σ5でのプロダクトオペレータを表示せよ。

CHのDEPT
σ1JSA

ωA

σ2-Ay cosωAt cosπJSAt ⇒ 0-Ay cosωAt

180°x(I),90°x(S)2AxSz cosωAt sinπJSAt ⇒ 2AxSz cosωAt ⇒ -2AxSy cosωAt-AyAx sinωAt cosπJSAt ⇒ 0Ax sinωAt

180°x(I),90°x(S)2AySz sinωAt sinπJSAt ⇒ 2AySz sinωAt ⇒ 2AySy sinωAt

CHのDEPTσ2ωA-2AxSy cosωAt cosωAt-2AxSy cosωAt-2AySy cosωAt sinωAt2AySy sinωAt cosωAt2AySy sinωAt+)-2AxSy sinωAt sinωAt-2AxSy (cosωAt cosωAt + sinωAt sinωAt)= -2AxSy

CHのDEPTωSJAS

σ3β°y(I),180°x(S)σ42AxSy cosωSt cosβ-2AxSy cosωSt ⇒ -2AxSy cosωSt-2AzSy cosωSt sinβ-2AxSy
2AxSx sinωSt cosβ2AxSx sinωSt ⇒ 2AxSx sinωSt-2AzSx sinωSt sinβ

CHのDEPTωSJAS

σ3β°y(I),180°x(S)σ42AxSy cosωSt cosβ-2AxSy cosωSt ⇒ -2AxSy cosωSt-2AzSy cosωSt sinβ-2AxSy2AxSx sinωSt cosβ
2AxSx sinωSt ⇒ 2AxSx sinωSt-2AzSx sinωSt sinβ

CHのDEPT
σ5JSA

ωS-2AzSy cosωSt cosωSt cosπJSAt sinβ ⇒ 0-2AzSy cosωSt cosωSt sinβ

Sx cosωSt cosωSt sinπJSAt sinβ
⇒ Sx cosωSt cosωSt sinβ-2AzSy cosωSt sinβ

2AzSx cosωSt sinωSt cosπJSAt sinβ ⇒ 02AzSx cosωSt sinωSt sinβ

Sy cosωSt sinωSt sinπJSAt sinβ
⇒ Sy cosωSt sinωSt sinβ-2AzSx sinωSt cosωSt cosπJSAt sinβ ⇒ 0-2AzSx sinωSt cosωSt sinβ-Sy sinωSt cosωSt sinπJSAt sinβ
⇒ -Sy sinωSt cosωSt sinβ-2AzSx sinωSt sinβ-2AzSy sinωSt sinωSt cosπJSAt sinβ ⇒ 0-2AzSy sinωSt sinωSt sinβ

Sx sinωSt sinωSt sinπJSAt sinβ+)⇒ Sx sinωSt sinωSt sinβ
Sx (cosωAt cosωAt + sinωAt sinωAt) sinβ
= Sx sinβCHのDEPT まとめβyI
1/2JIS1/2JIS1/2JIS

S
σ1 σ2

σ3 σ4

σ5

１．化学シフト項は全てリフォーカスする。
２．Jカップリング項のみ計算する。
３．σ4でIスピンがx,y成分のときはリフォーカスしない。

CH2のDEPT
βyI
1/2JIS

1/2JIS1/2JIS

S
σ1 σ2

σ3 σ4

σ5

Q6. I2Sスピン系において、σ1でのプロダクトオペレータを表示せよ。
Q7. I2Sスピン系において、σ2でのプロダクトオペレータを表示せよ。
Q8. I2Sスピン系において、σ3でのプロダクトオペレータを表示せよ。
Q9. I2Sスピン系において、σ4でのプロダクトオペレータを表示せよ。
Q10. I2Sスピン系において、σ5でのプロダクトオペレータを表示せよ。

CH2のDEPT-Ay

180°x(I),90°x(S)

β°y(IA),180°x(S)2AxSz ⇒ -2AxSy

β°y(IB)
4AxSxBz-4AzSxBz sinβ cosβ-4AzSxBz sinβ

JSA

σ1

σ2JSB σ3

σ4

CH2のDEPT-4AzSxBz sinβ cosβ-2SyBz sinβ cosβSx sinβ cosβσ4JSAJSB

σ5

CH3のDEPT 演習
βyI
1/2JIS

1/2JIS1/2JIS

S
σ1 σ2

σ3 σ4

σ5

Q11. I3Sスピン系において、σ1でのプロダクトオペレータを表示せよ。
Q12. I3Sスピン系において、σ2でのプロダクトオペレータを表示せよ。
Q13. I3Sスピン系において、σ3でのプロダクトオペレータを表示せよ。
Q14. I3Sスピン系において、σ4でのプロダクトオペレータを表示せよ。
Q15. I3Sスピン系において、σ5でのプロダクトオペレータを表示せよ。

CH3のDEPT-Ay

180°x(I),90°x(S)2AxSz ⇒ -2AxSy
4AxSxBz
8AxSyBzCz

JSAσ1σ2JSB

JSC

σ3

CH3のDEPT
β°y(IA),180°x(S)

β°y(IC)β°y(IB)

4AxSyBzCz

4AzSyBzCz sinβ cos2β

4AzSyBzCz sinβ cosβ
4AzSyBzCz sinβσ3σ4CH3のDEPT

4AzSyBzCz sinβ cos2β-2SxBzCz sinβ cos2β-2SyCz sinβ cos2β
Sx sinβ cos2β

σ4

JSAJSB

JSC

σ5

DEPTQ
βyI
1/2JIS

1/2JIS

1/2JIS

DEPT
1-3級13Cの検出

1/2JIS

DEPTQ
4級13Cの検出も可能

S

βyI-yS

1/2JIS

1/2JIS

1/2JIS-x

DEPTQ ４級13Cスペクトル
COMMUNICATIONS

533DEPTQ

13C 1DFIG. 2. Comparison of the DEPTQ, SEMUT, SEMUT-90, and the one-pulse 13C (reference) experiments applied to eugenol dissolved in acetone-d6 andperformed on a BRUKER DRX-400 spectrometer, with 90° pulse lenghts of 9.1 and 6.2 us for 1H and 13C respectively. The DEPTQ and SEMUT experiments
were set up and applied for complete spectral editing as described in the text, whereas SEMUT-90, yielding exclusively the signals of quaternary carbons, wasapplied for comparison. Several subexperiments with different 1H selection pulses were performed with DEPTQ and SEMUT, and the corresponding data werestored separately. The same relaxation delay (D1 ! 2 s) and the same delay for coupling evolution (D2 ! 3.45 ms) were used throughout. An equal total numberof scans were acquired within the same total measuring time with each experiment. As a result the corresponding Cq subspectra (expansion 110 –150ppm)
obtained with DEPTQ (A), SEMUT (B), and SEMUT-90 (C) are shown together with the corresponding spectrum of the one-pulse experiment (D). The residual
signal at 115.2 ppm, visible in all edited spectra, originates from the olefinic methylene group.

combined application of the basic “CHn-only” DEPT experiment and SEMUT-90 recommended in the literature. Although many of the more routine problems with molecular

structures may be solved by partial instead of complete
editing of carbon spectra, performing well-established methods such as APT, SEMUT-180, DEPT-135, or no editing at

Burger R and Bigler P,
J Magn Reson, 1998.

PENDANTyI
1/4JIS

1/4JIS(1/4JIS)(1/4JIS)(1/4JIS)(1/4JIS)refocused INEPT
1-3級13Cの検出

S-yI
1/4JISS

1/4JIS-yPENDANT
4級13Cの検出も可能

niques. A sequence is described here that embodies
tages of both techniques by enabling polarizationent that is nurtured during attached nucleus testingNT).
PT sequence relies on the evolution of spin-spin
ingle quantum coherence transition magnetizationachieve alternating signs of signals from quaternary,
methylene and methyl group 13C nuclei. Irradiationlei can result in a significant NOE enhancement ofances from the last three functional groups by ao 1.998. Quaternary 13C resonances normally showncement. The spin-lattice relaxation times (TI) ofved nuclei govern the inter-pulse sequence delay
T1). As Tl for quaternary 13C can be several tens ofmuch lower than ideal inter-sequence delay is often
at all, particularly the quaternary 13C, resonances
ed in intensity.
tion transfer from 1H to 13C can be used both to3C signal intensities and transfer the dependence ofequence delay onto the shorter 1H Tls. If convenarization transfer to all relevant carbon nuclei issimultaneously, the problem of refocusing
normal evolution delays) all spin-coupled comf individual nuclei in the same phase sense, whilePENDANT
quaternary 13C resonances, might
appear intractdoubtedly, this problem impinged on the use ofquantum coherence transitions' in the DEPT
Although this does not permit the simultaneousof quaternary 13C, it does have the advantage ofpolarization transfer to varying degrees so thatthe observed spectra may be achieved with similar
APT.
ly, there is a need for a pulse sequence that results inn enhanced and edited spectra that contain resom all detectable nuclei. This is possible through theof single quantum coherence DEPT-135
transitions and theolarization transfer principles implicit in PENe pulse sequence for which is as follows:)n(+x)
d2(-y)
1/4J n(+n) 1/4J n/2(-y)
BCDEz-axis and the 13C pulse may, for simplicity, be considered toreturn the magnetization components of 13C nuclei strongly
coupled to protons, opposed back to the +x-axes. Steps F-H
allow vector evolution to suitable orientations for chemicalshift refocusing and detection. Ignoring the small changes tothe evolution angles that the preceding steps introduce, thequaternary and methylene 13C vectors would become aligned
along the +y-axis prior to decoupling and detection, with themethyne and methyl vectors at 45" to the -y-axis. Before

PENDANT

4級13Cの検出も可能

n(+x)
decouple
5/81 n ( + x ) 5/81 acquire
FGH

h the details of this will be explained elsewhere,
ures will now be explained in simplified outline, withto the normal NMR rotating frame of reference
rection of polarizing magnetic field; y-axis, detecassuming that the frequency of the rotating frame isct chemical shift frequency for each resonance.

Fig. 1 Comparison of the 'H-decoupled ( a ) APT (with NOE), (6)PENDANT (not phase cycled) and ( c ) DEPT (135") 13C spectra ofethylbenzene under equivalent conditions

Homer J and Perry MC,
Chem Commun, 1994.