The Improved Solid-state NMR Quantitative Method on the Bases of Multiple-cross Polarization Technique

doi:10.11938/cjmr20223039

Abstract

Abstract:

Recently, multiple-cross polarization (multiCP) has attracted much interest owing to its favorable performance as a solid-state nuclear magnetic resonance quantitative method. Relating investigations revealed that the setup of multiCP parameters relies on the properties of the samples. Diverse types of samples require different parameters. To improve the tolerance to sample properties, an improved method named MLGCP-1 was proposed in this work, which employed Lee-Goldburg cross polarization technique. L-alanine, L-valine and their mixtures were chosen as model samples to evaluate the performance of MLGCP-1 method. multiCP experiments were also conducted for comparison. Based on the test of molecular group ratio, it was revealed that the range of contact time t_p of MLGCP-1 was larger than that of multiCP, which improved from 1.0~1.3 ms to 0.8~2.0 ms. Moreover, according to the study of L-valine and mixtures, it was revealed that the range of t_p was influenced by the difference of cross relaxation time T_CH. Large T_CHdifference limited t_prange for quantification. This manner was in accordance with multiCP. However, the t_prange of MLGCP-1 was markedly enlarged in comparison with multiCP, presenting higher tolerance to the sample properties.

Key words: solid-state nuclear magnetic resonance (SSNMR), cross polarization, multiCP, quantitative method, amino acid

CLC Number:

O482.53

DONG Hongchun,ZHANG Zhilan,WANG Ning,TANG Dandan,QIU Zihui,SHU Jie. The Improved Solid-state NMR Quantitative Method on the Bases of Multiple-cross Polarization Technique[J]. Chinese Journal of Magnetic Resonance, 2023, 40(2): 136-147.

Figures/Tables 10

Fig. 1

Fig. 2

Table 1

TCH and T 1 ρ Hvalues of L-alanine and L-valine measured under ramp-CP and LGCP conditions

Sample	Carbons	T_1,H/ms	ramp-CP		LGCP
Sample	Carbons	T_1,H/ms	T_CH/ms	$T 1 ρ H$ /ms	T_CH/ms	$T 1 ρ H$ /ms
L-alanine	1	977.1	0.170	1.7	0.387	12.8
	2		0.042		0.174
	3		0.360		0.331
L-valine	4	718.5	0.174	2.5	0.414	24.3
	5		0.036		0.157
	6		0.033		0.120
	7		0.290		0.240
	8		0.154		0.374

Table 1

Fig. 3

Fig. 4

Fig. 5

Fig. 6

Fig. 7

Fig. 8

Table 2

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样品组分	t_p/ms	MLGCP-1百分误差/%			multiCP百分误差/%
样品组分	t_p/ms	2/5	2/6	3/6	2/5	2/6	3/6
1:3	0.5	1.29	0.94	14.4	4.54	4.40	18.2
	1.0	1.80	4.57	4.53	0.85	8.35	10.2
	1.5	4.91	3.88	4.05	0.22	12.5	28.5
	2.0	3.63	1.27	10.1	0.58	18.7	51.0
1:1	0.5	1.24	1.84	9.67	0.49	1.31	20.1
	1.0	1.33	1.40	3.16	1.14	2.14	3.96
	1.5	1.09	1.13	3.54	0.83	2.63	12.7
	2.0	0.77	0.85	4.40	3.71	0.70	23.1
3:1	0.5	0.72	2.09	6.99	2.31	0.46	11.9
	1.0	2.14	1.76	2.34	0.68	4.99	4.09
	1.5	0.06	1.05	1.10	0.72	7.29	9.63
	2.0	0.92	1.48	0.74	0.74	9.98	14.2