Preparation and evaluation of diureido bridged β-cyclodextrin-bonded chiral stationary phase by high-performance liquid chromatography

doi:10.3724/SP.J.1123.2019.08006

Abstract

Abstract:

A diureido bridged β-cyclodextrin dimer was synthesized by the reaction of 6-deoxy-6-hydroxyethylamino-β-cyclodextrin with hexamethylene diisocyanate. The dimer was then bonded onto silica to obtain a novel diureido bridged β-cyclodextrin-bonded stationary phase (UBCDP). The structure of diureido bridged stationary phase was characterized by infrared spectroscopy, mass spectrometry, and elemental analysis. By using racemic drugs and pesticides as probes (flavanones, triazoles, and dansylated amino acids), the chromatographic properties of UBCDP were evaluated. The separation mechanism was elucidated by comparison with a single β-cyclodextrin chiral stationary phase (CDCSP). The composition, pH value of the mobile phase and column temperature were optimized. The results showed that the UBCDP can resolve 25 chiral compounds, especially 2'-hydroxyflavanone, hexaconazole and dansyl leucine with high resolutions (R_s, 1.52-4.35), and the larger volume hesperidin could also be separated. This trend was related to the synergistic inclusion of bridged cyclodextrins. CDCSP can separate only a small number of enantiomers with low resolutions. UBCDP exhibited better enantio-separation ability and hence had potential application in chiral drugs and chiral pesticide residues analysis.

Key words: high performance liquid chromatography (HPLC), diureido bridged β-cyclodextrin-bonded stationary phase (UBCDP), chiral drug and pesticide separations, chromatographic performance evaluation, chromatographic separation mechanism

CLC Number:

O658

SHUANG Yazhou, WANG Hui, ZHANG Tianci, LI Laisheng. Preparation and evaluation of diureido bridged β-cyclodextrin-bonded chiral stationary phase by high-performance liquid chromatography[J]. Chinese Journal of Chromatography, 2020, 38(4): 464-475.

Figures/Tables 14

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Compound	k₁	k₂	k₃	R_s1	R_s2	Elution order	CSP
Nitroaniline	1.80	1.96	5.13	1.45	17.78	m-o-p	UBCDP
	0.80	1.27	3.84	2.40	11.44	m-o-p	CDCSP
Phenylenediamine	0.16	0.66	1.41	4.58	3.68	m-p-o	UBCDP
	0.20	/	/	/	/	/	CDCSP
Phthalic acid	0.69	2.67	8.11	17.15	23.68	m-p-o	UBCDP
	1.70	2.37	7.42	8.93	10.57	m-p-o	CDCSP

Compound	k₁	k₂	k₃	R_s1	R_s2	Elution order	CSP
Nitroaniline	1.80	1.96	5.13	1.45	17.78	m-o-p	UBCDP
	0.80	1.27	3.84	2.40	11.44	m-o-p	CDCSP
Phenylenediamine	0.16	0.66	1.41	4.58	3.68	m-p-o	UBCDP
	0.20	/	/	/	/	/	CDCSP
Phthalic acid	0.69	2.67	8.11	17.15	23.68	m-p-o	UBCDP
	1.70	2.37	7.42	8.93	10.57	m-p-o	CDCSP

Compound	k₁	k₂	α	R_s	Mobile phase	Column
Flavanone	3.57	4.02	1.12	1.47	1%HCOOH/ACN (90/10, v/v)	UBCDP
	3.13	/	/	0	1%HCOOH/ACN (80/20, v/v)	CDCSP
2'-Hydroxy flavanone	2.33	3.27	1.40	4.35	1%HCOOH/MeOH (75/25, v/v)	UBCDP
	3.34	3.53	1.05	1.67	1%HCOOH/MeOH (85/15, v/v)	CDCSP
4'-Hydroxy flavanone	3.61	4.38	1.22	3.47	1%HCOOH/ACN (90/10, v/v)	UBCDP
	9.59	10.01	1.04	0.66	1%HCOOH/MeOH (85/15, v/v)	UBCDP
	4.88	/	/	0	1%HCOOH/ACN (80/20, v/v)	CDCSP
6-Hydroxy flavanone	5.18	5.59	1.08	1.14	1%HCOOH/MeOH (85/15, v/v)	UBCDP
	9.89	/	/	0	1%HCOOH/MeOH (90/10, v/v)	CDCSP
6-Methoxy flavanone	6.88	7.33	1.07	1.06	1%HCOOH/MeOH (70/30, v/v)	UBCDP
	6.57	/	/	0	1%HCOOH/MeOH (90/10, v/v)	CDCSP
Naringin	2.61	3.18	1.22	2.73	1%HCOOH/MeOH (80/20, v/v)	UBCDP
	4.12	4.54	1.10	1.12	1%HCOOH/MeOH (80/20, v/v)	CDCSP
Hesperidin	2.45	2.81	1.15	1.34	1%HCOOH/ACN (90/10, v/v)	UBCDP
	4.83	/	/	0	1%HCOOH/MeOH(80/20, v/v)	CDCSP
Catechin	3.29	3.82	1.16	2.46	1%HCOOH/ACN (90/10, v/v)	UBCDP
	4.16	4.62	1.19	1.36	1%HCOOH/ACN (85/15, v/v)	CDCSP

Compound	k₁	k₂	α	R_s	Mobile phase	Column
Flavanone	3.57	4.02	1.12	1.47	1%HCOOH/ACN (90/10, v/v)	UBCDP
	3.13	/	/	0	1%HCOOH/ACN (80/20, v/v)	CDCSP
2'-Hydroxy flavanone	2.33	3.27	1.40	4.35	1%HCOOH/MeOH (75/25, v/v)	UBCDP
	3.34	3.53	1.05	1.67	1%HCOOH/MeOH (85/15, v/v)	CDCSP
4'-Hydroxy flavanone	3.61	4.38	1.22	3.47	1%HCOOH/ACN (90/10, v/v)	UBCDP
	9.59	10.01	1.04	0.66	1%HCOOH/MeOH (85/15, v/v)	UBCDP
	4.88	/	/	0	1%HCOOH/ACN (80/20, v/v)	CDCSP
6-Hydroxy flavanone	5.18	5.59	1.08	1.14	1%HCOOH/MeOH (85/15, v/v)	UBCDP
	9.89	/	/	0	1%HCOOH/MeOH (90/10, v/v)	CDCSP
6-Methoxy flavanone	6.88	7.33	1.07	1.06	1%HCOOH/MeOH (70/30, v/v)	UBCDP
	6.57	/	/	0	1%HCOOH/MeOH (90/10, v/v)	CDCSP
Naringin	2.61	3.18	1.22	2.73	1%HCOOH/MeOH (80/20, v/v)	UBCDP
	4.12	4.54	1.10	1.12	1%HCOOH/MeOH (80/20, v/v)	CDCSP
Hesperidin	2.45	2.81	1.15	1.34	1%HCOOH/ACN (90/10, v/v)	UBCDP
	4.83	/	/	0	1%HCOOH/MeOH(80/20, v/v)	CDCSP
Catechin	3.29	3.82	1.16	2.46	1%HCOOH/ACN (90/10, v/v)	UBCDP
	4.16	4.62	1.19	1.36	1%HCOOH/ACN (85/15, v/v)	CDCSP

Compound	k₁	k₂	α	R_s	Mobile phase	Column
Dns-Leu	1.52	1.79	1.17	1.69	1% TEAA/MeOH/ACN (70/25/5, v/v/v, pH 4.0)	UBCDP
	1.16	1.21	1.04	0.79	1% TEAA/MeOH/ACN (80/15/5, v/v/v, pH 4.0)	CDCSP
Dns-Phe	5.13	6.42	1.25	2.07	1% TEAA/MeOH/ACN (70/25/5, v/v/v, pH 4.0)	UBCDP
	1.75	1.82	1.04	0.87	1% TEAA/MeOH/ACN (80/15/5, v/v/v, pH 4.0)	CDCSP
Dns-Asp	2.63	2.97	1.12	1.32	1% TEAA/MeOH/ACN (70/25/5, v/v/v, pH 4.0)	UBCDP
	1.24	1.34	1.08	0.82	1% TEAA/MeOH/ACN (80/15/5, v/v/v, pH 4.0)	CDCSP
Dns-Met	1.91	2.14	1.12	1.25	1% TEAA/MeOH/ACN (70/25/5, v/v/v, pH 4.0)	UBCDP
	1.49	1.58	1.06	0.70	1% TEAA/MeOH/ACN (80/15/5, v/v/v, pH 4.0)	CDCSP
Dns-Tyr	1.11	1.18	1.07	0.78	1% TEAA/MeOH/ACN (70/25/5, v/v/v, pH 4.0)	UBCDP
	1.37	/	/	/	1% TEAA/MeOH/ACN (80/15/5, v/v/v, pH 4.0)	CDCSP
Dns-Thr	2.08	2.37	1.62	0.73	1% TEAA/MeOH/ACN (70/25/5, v/v/v, pH 4.0)	UBCDP
	1.37	/	/	<0.50	1% TEAA/MeOH/ACN (80/15/5, v/v/v, pH 4.0)	CDCSP
Dns-Ser	4.01	4.07	1.01	0.63	1% TEAA/MeOH/ACN (70/25/5, v/v/v, pH 4.0)	UBCDP
	1.47	/	/	<0.50	1% TEAA/MeOH/ACN (80/15/5, v/v/v, pH 4.0)	CDCSP
Dns-Ala	3.34	3.37	1.01	0.85	1% TEAA/MeOH/ACN (70/25/5, v/v/v, pH 4.0)	UBCDP
	2.19	2.21	1.01	0.65	1% TEAA/MeOH/ACN (80/15/5, v/v/v, pH 4.0)	CDCSP