Enantioseparations of Triazole Chiral Pesticides on Two β-Cyclodextrin-bonded Stationary Phases with Different Linkages by HPLC†

doi:10.7503/cjcu20141095

Abstract

Abstract:

Two kinds of new β-cyclodextrin-bonded chiral stationary phases(CDSP and NCDSP) with carbamate and urea linkages were prepared using ordered mesoporous material SBA-15 as matrix, β-cyclodextrin and 6-amino β-cyclodextrin as ligands via the addition reactions of OH and NH₂ groups of β-cyclodextrin with active 3-isocyanatopropyltriethoxy silane, respectively. The enantioseparation properties of two new stationary phases were evaluated and compared by adopting 10 kinds of common chiral triazole pesticides as probes including triticonazole, diniconazole, hexaconazole, tebuconazole, etc. in reversed-phase mode. The results show that CDSP and NCDSP exhibited excellent and fast chiral separation ability for triazole pesticides within 30 min. Nine and eight kinds of triazole enantiomers were separated on CDSP and NCDSP at room temperature with methanol/H₂O and acetonitrile/H₂O as mobile phase, respectively. The chiral selectivity factor(α) are 1.29 for triticonazole with a resolution of 3.84 for CDSP and 1.28 for diniconazole with a resolutions of 3.23 for NCDSP. It was found that triazole pesticides with appropriate size and —OH groups on CDSP and NCDSP had better separation effect, indicating that the inclusion, hydrogen bonding, steric hindance and other synergic forces between β-cyclodextrin ligand and solutes could contribute enantioseparations. The surface loading of CDSP and NCDSP by different batches were 0.139—0.156 and 0.120—0.137 μmol/m², respectively, indicating that the new preparation methods have good reproducibility. Compared with the commodity coated cellulose column, the new cyclodextrin stationary phases with urea and carbamate linkages were more stable, more practical, easy preparation and low cost. The prepared β-cyclodextrin stationary phases have good prospects in the enantiomeric monitoring of triazole pesticides residues.

Key words: High performance liquid chromatography, β, -Cyclodextrin-based SBA-15 stationary phase, Triazole chiral pesticide, Enantioseparation, Separation mechanism

CLC Number:

O657

TrendMD:

CHENG Biaoping, LI Laisheng, ZHOU Rendan, LI Liang, ZHANG Hongfu. Enantioseparations of Triazole Chiral Pesticides on Two β-Cyclodextrin-bonded Stationary Phases with Different Linkages by HPLC^†[J]. Chem. J. Chinese Universities, 2015, 36(5): 872.

Figures/Tables 9

References 20

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CSP phase	EA(%)			Surface loading^a/(μmol·m^-2)	TGA, w(%)	Surface loading^b/(μmol·m^-2)
CSP phase	C			Surface loading^a/(μmol·m^-2)	H	N
CDSP	3.61	0.89	0.33	0.156	8.2	0.149
NCDSP	3.17	1.03	0.30	0.137	7.1	0.129

CSP phase	EA(%)			Surface loading^a/(μmol·m^-2)	TGA, w(%)	Surface loading^b/(μmol·m^-2)
CSP phase	C			Surface loading^a/(μmol·m^-2)	H	N
CDSP	3.61	0.89	0.33	0.156	8.2	0.149
NCDSP	3.17	1.03	0.30	0.137	7.1	0.129

Pesticide	k'₁	k'₂	α₁	R_s1	k'₃	k'₄	α₂	R_s2	Mobile phase(volume ratio)	Column	Ref.
Triticonazole	9.06	11.66	1.29	3.84					H₂O/ACN(75/25)	CDSP
	10.58	10.79	1.02	0.66					H₂O/ACN(82.5/17.5)	NCDSP
Diniconazole	11.23	14.42	1.28	3.23					H₂O/ACN(77.5/22.5)	CDSP
	5.76	6.37	1.11	1.50					H₂O/ACN(80/20)	NCDSP
				2.75					H₂O/MeOH(20/80)	ADMPC^*	[19]
				1.31					H₂O/ACN(50/50)	CDMPC^*	[19]
Tebuconazole	4.69	5.72	1.22	2.66					H₂O/ACN(72.5/27.5)	CDSP
	5.59	5.98	1.07	1.35					H₂O/ACN(80/20)	NCDSP
				1.30					H₂O/ACN(50/50)	ADMPC	[19]
				0					H₂O/ACN(50/50)	CDMPC	[19]
Hexaconazole	7.85	8.77	1.12	1.77					H₂O/ACN(80/20)	CDSP
	9.17	10.1	1.17	2.42					H₂O/ACN(85/15)	NCDSP
				1.28					H₂O/ACN(55/45)	ADMPC	[19]
				1.72					H₂O/ACN(50/50)	CDMPC	[19]
Flutriafol	3.42	3.96	1.16	1.74					H₂O/MeOH(65/35)	CDSP
	6.91	7.87	1.14	1.79					H₂O/MeOH(80/20)	NCDSP
				1.05					H₂O/MeOH(30/70)	ADMPC	[19]
				0					H₂O/MeOH(30/70)	CDMPC	[19]
Uniconazole	14.35	15.54	1.08	1.19					H₂O/ACN(80/20)	CDSP
	8.19	8.59	1.05	0.69					H₂O/ACN(82.5/17.5)	NCDSP
				2.41					H₂O/ACN(40/60)	ADMPC	[19]
				0					H₂O/ACN(40/60)	CDMPC	[19]
Imazalil	6.00	6.40	1.07	0.84					0.1%TEAA/ACN	CDSP
									(70/30), pH=5.0
	6.74	7.38	1.09	1.30					0.1%TEAA/ACN	NCDSP
									(82.5/17.5), pH=5.0
Myclobutanil	7.85	8.77	1.03	<0.5					H₂O/ACN(85/15)	CDSP
	8.34	8.34	1.00	0					H₂O/ACN(90/10)	NCDSP
Triadimenol	5.27	5.27	1.00	0	10.33	11.2	1.08	1.01	H₂O/ACN(75/25)	CDSP
	4.82	5.23	1.09	1.35	7.96	8.30	1.04	<0.5	H₂O/ACN(82.5/17.5)	NCDSP
Triadimefon	10.00	10.00	1.00	0					H₂O/ACN(80/20)	CDSP
	8.00	8.00	1.00	0					H₂O/ACN(85/15)	NCDSP
				0					H₂O/MeOH(20/80)	ADMPC	[19]
				1.35					H₂O/MeOH(20/80)	CDMPC	[19]

Pesticide	k'₁	k'₂	α₁	R_s1	k'₃	k'₄	α₂	R_s2	Mobile phase(volume ratio)	Column	Ref.
Triticonazole	9.06	11.66	1.29	3.84					H₂O/ACN(75/25)	CDSP
	10.58	10.79	1.02	0.66					H₂O/ACN(82.5/17.5)	NCDSP
Diniconazole	11.23	14.42	1.28	3.23					H₂O/ACN(77.5/22.5)	CDSP
	5.76	6.37	1.11	1.50					H₂O/ACN(80/20)	NCDSP
				2.75					H₂O/MeOH(20/80)	ADMPC^*	[19]
				1.31					H₂O/ACN(50/50)	CDMPC^*	[19]
Tebuconazole	4.69	5.72	1.22	2.66					H₂O/ACN(72.5/27.5)	CDSP
	5.59	5.98	1.07	1.35					H₂O/ACN(80/20)	NCDSP
				1.30					H₂O/ACN(50/50)	ADMPC	[19]
				0					H₂O/ACN(50/50)	CDMPC	[19]
Hexaconazole	7.85	8.77	1.12	1.77					H₂O/ACN(80/20)	CDSP
	9.17	10.1	1.17	2.42					H₂O/ACN(85/15)	NCDSP
				1.28					H₂O/ACN(55/45)	ADMPC	[19]
				1.72					H₂O/ACN(50/50)	CDMPC	[19]
Flutriafol	3.42	3.96	1.16	1.74					H₂O/MeOH(65/35)	CDSP
	6.91	7.87	1.14	1.79					H₂O/MeOH(80/20)	NCDSP
				1.05					H₂O/MeOH(30/70)	ADMPC	[19]
				0					H₂O/MeOH(30/70)	CDMPC	[19]
Uniconazole	14.35	15.54	1.08	1.19					H₂O/ACN(80/20)	CDSP
	8.19	8.59	1.05	0.69					H₂O/ACN(82.5/17.5)	NCDSP
				2.41					H₂O/ACN(40/60)	ADMPC	[19]
				0					H₂O/ACN(40/60)	CDMPC	[19]
Imazalil	6.00	6.40	1.07	0.84					0.1%TEAA/ACN	CDSP
									(70/30), pH=5.0
	6.74	7.38	1.09	1.30					0.1%TEAA/ACN	NCDSP
									(82.5/17.5), pH=5.0
Myclobutanil	7.85	8.77	1.03	<0.5					H₂O/ACN(85/15)	CDSP
	8.34	8.34	1.00	0					H₂O/ACN(90/10)	NCDSP
Triadimenol	5.27	5.27	1.00	0	10.33	11.2	1.08	1.01	H₂O/ACN(75/25)	CDSP
	4.82	5.23	1.09	1.35	7.96	8.30	1.04	<0.5	H₂O/ACN(82.5/17.5)	NCDSP
Triadimefon	10.00	10.00	1.00	0					H₂O/ACN(80/20)	CDSP
	8.00	8.00	1.00	0					H₂O/ACN(85/15)	NCDSP
				0					H₂O/MeOH(20/80)	ADMPC	[19]
				1.35					H₂O/MeOH(20/80)	CDMPC	[19]

Column	T/K	1/T	k₁'	k₂'	α	lnα	R_s	Mobile phase(volume ratio)
CDSP	293	0.003413	7.85	8.77	1.12	0.1133	1.77	H₂O/ACN(80/20)
	298	0.003356	6.20	6.85	1.10	0.0953	1.57
	303	0.003300	5.27	5.75	1.09	0.0862	1.42
	308	0.003247	4.46	4.81	1.08	0.0770	1.23
	313	0.003195	3.79	4.05	1.07	0.0677	1.08
NCDSP	293	0.003413	9.17	10.71	1.17	0.1570	2.42	H₂O/ACN(85/15)
	298	0.003356	6.72	7.68	1.14	0.1310	2.02
	303	0.003300	5.70	6.41	1.12	0.1133	1.82
	308	0.003247	4.74	5.27	1.11	0.1044	1.63
	313	0.003195	3.99	4.37	1.10	0.0953	1.42