Time-saving and Highly Applicable Quantitative Method Based on Solid-state Nuclear Magnetic Resonance Techniques†

doi:10.7503/cjcu20170323

Abstract

Abstract:

For most solid samples, direct polarization(DP) consumes extraordinarily long time. QCP/QCP_RC method was capable to provide quantitative information in notably short period of time. However, QCP/QCP_RC was not applicable for systems with long or under high MAS frequency condition. To solve aforementioned problems, rCDPz sequence was designed and rQCPz/rQCPz^RC method was proposed. L-Alanine, L-histidine and their mixtures were used to evaluate the accuracy of rQCPz/rQCPz^RC method. By comparing among three schemes of cross polarization(CP), DP and rQCPz/rQCPz^RC, it is demonstrated that rQCPz/rQCPz^RC provides accuracy equal to that of DP experiment but consumes markedly shorter experimental time.

Key words: Solid-state NMR, Quantification, Cross polarization, Cross depolarization

CLC Number:

O657.61

TrendMD:

GU Jiali, ZHANG Tiantian, ZHAO Huipeng, SHU Jie, LI Xiaohong. Time-saving and Highly Applicable Quantitative Method Based on Solid-state Nuclear Magnetic Resonance Techniques^†[J]. Chem. J. Chinese Universities, 2018, 39(3): 463.

Figures/Tables 8

Fig.1 Pulse sequence schemes of cross polarization(CP) experiment(A), direct polarization(DP) experiment(B) and cross depolarization(CDP) experiment(C)tp: Contact time for preparing the polarized 13C signal; td: duration for the dephase of 1H transverse magnetization; tCP: CP/CDP contact time.

Fig.2 Pulse sequences employed in rQCPz method(A) rCP pulse sequence; (B) rCDPz pulse sequence.

Fig.3 Structural schemes of L-alanine and L-histidine molecules(A) and 13C{1H} rCP spectra of L-alanine(a), L-histidine(b) and their mixture(c)(B) Peaks are assigned with respect to the labels in structural schemes.

Fig.4 rCP(t), rCDP(t) and sum(t) curves of —CH3 in L-alanine, demonstrating the reciprocity relation between rCP and rCDPz(A) and the relaxation compensated rCPRC(t), rCDPRC(t) and sumRC(t) curves of —CH3 in L-alanine demonstrating the reciprocity relation between rCP and rCDPz with relaxation compensation(B)The function for relaxation compensation was f(t)=1-0.78735t.

Fig.5 13C rCP(t), rCDPz(t) and sum(t) curves of carbon sites —Cd(A) and —Ce(B) in L-histidine

Table 1 Measurement results, errors and experimental time of L-alanine obtained by CP, DP as well as rQCPz/rQCPzRC methods

Technology/method	T_CP/μs	Molar fraction			Percentage error(%)	Time/h
Technology/method	T_CP/μs	CO			CH	CH₃
CP	220	0.27	1.66	1.07	±73	0.2
DP		0.99	0.96	1.05	±5	4.63
rQCPz	220	1.04	0.93	1.03	±7	0.6
	420	1.07	0.90	1.06	±10	0.6
rQCPz^RC	220	1.00	0.95	1.05	±5	1.0
	420	1.04	0.92	1.04	±8	1.0
Theoretical value		1	1	1

Table 2 Measurement results, errors and experimental time of L-histidine obtained by CP, DP as well as rQCPz methods

Technology/method	Molar fraction						Percentage error(%)	Time/h
Technology/method	C_a			C_f	C_d	C_e	C_b	C_c
CP	0.58	0.86	0.95	1.03	1.23	1.35	±42	0.37
DP	1.09	1.11	0.93	0.93	1.01	0.95	±11	142.2
rQCPz	0.99	1.08	0.97	0.99	1.03	0.95	±8	1.1
Theoretical value	1	1	1	1	1	1

Table 3 Measurement results, errors and experimental time of L-alanine/L-histidine mixture obtained by using CP, DP as well as rQCPz methods

Technology/method	n(Ala)/n(His)	Relative error(%)	Time/h
CP	0.497	±31.9	1
DP	0.730		422
rQCPz	0.747	±2.3	3

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