Sepatation of Antipyretic Analgesics by CapillaryElectrochromatography with Block Copolymer Coating†

doi:10.7503/cjcu20170853

Abstract

Abstract:

A unique open tubular capillary electrochromatography(OT-CEC) system with block copolymer coating was constructed for separation of antipyretic analgesics. The amphipathic poly(maleic anhydride-co-styrene) was synthesized by reversible addition-fragmentation chain transfer polymerization method. The effects of several key factors on the OT-CEC separation efficiency were investigated. Interestingly, by adding organic solvent to the running buffer, the block copolymer coating could self-assemble to form micelle-like spheres and play the role of surfactants. Comparing with the bare capillary, the coating one could enhance the separation efficiency obviously. Moreover, the results indicated that the coating capillaries had a good stability and repeatability. Under the optimized OT-CEC conditions, the developed OT-CEC assay was used to ananlyze the antipyretic drugs in clinical tables with satisfactory linearity(R²≥0.988). The detection limits obtained from the calculations based on signal-to-noise ratio(S/N=3) were 3.5—4.8 μg/mL for the test drugs.

Key words: Open tubular capillary electrochromatography, Block copolymer coating, Antipyretic analgesics

CLC Number:

O657.8

TrendMD:

FENG Wenya, QIAO Juan, QI Li, LI Zhiwei. Sepatation of Antipyretic Analgesics by CapillaryElectrochromatography with Block Copolymer Coating^†[J]. Chem. J. Chinese Universities, 2018, 39(8): 1640.

Figures/Tables 9

Fig.1 Structures of the three test antipyretic analgesics

Fig.2 Coating process of the block copolymer(A), SEM images of the block copolymer coated capillary(B) and bare capillary(C)

Fig.3 TEM image of P(MAn-co-St)53-b-PSt224 in water

Table 1 Reproducibility of the analytes(n=6)

Analyte	Run-to-run RSD(%)		Day-to-day RSD(%)		Column-to-column RSD(%)
Analyte	Migration time, min	Peak area, μV·s	Migration time, min	Peak area, μV·s	Migration time, min	Peak area, μV·s
4-APP	0.68	1.29	1.03	1.31	2.16	2.14
DMAP	1.02	1.26	1.41	2.00	2.04	2.56
PH	1.38	1.49	1.72	1.52	2.25	2.34

Fig.4 Electropherograms of antipyretic analgesics under different capillary conditions(A) Bare capillary; (B) bare capillary with 40.0 mmol/L sodium dodecyl sulfate(SDS) in running buffer; (C) coated capillary without THF in running buffer; (D) coated capillary with 15.0% THF in running buffer. Buffer: 40.0 mmol/L KH2PO4, 10.0 mmol/L Na2B4O7 at pH=5.5. Experimental conditions: coating capillary: 75 μm i.d × 60 cm(45 cm effective); sampling: siphoned for 8 s at 15.0 cm height; voltage: 11.0 kV; UV detection: 254 nm. Peak 1: 4-AAP(0.2 mg/mL); peak 2: DMAP(0.2 mg/mL); peak 3: PH(0.2 mg/mL).

Fig.5 OT-CEC mechanism illustration for drugs analysis with the block copolymer coating

Table 2 Quantitation features of the three analytes(n=3)

Sample	Linear equation	R²	Linear range/(μg·mL^-1)	LOD/(μg·mL^-1)
4-AAP	y=9.3×10³x+4.5×10⁵	0.988	8.0—800.0	3.6
DMAP	y=5.1×10³x-2.0×10⁴	0.997	5.0—800.0	4.8
PH	y=3.6×10³x+1.6×10⁵	0.999	25.0—300.0	3.5

Table 3 Recoveries of DMAP and PH in tablets(n=3)

Analyte		Amount/(mg·mL^-1)	Addition/(mg·mL^-1)	Detection/(mg·mL^-1)	Recovery(%)
Sample 1	DMAP	0.31	0.25	0.58	108.0±5.1
	PH	0.10	0.08	0.17	112.9±3.9
Sample 2	DMAP	0.31	0.31	0.66	99.2±5.3
	PH	0.10	0.10	0.20	102.1±2.4
Sample 3	DMAP	0.31	0.37	0.71	107.5±3.6
	PH	0.10	0.12	0.22	102.0±1.5

Table 4 Determination of DMAP and PH in tablets(n=3)

Sample	DMAP(mg/tablet)	PH(mg/tablet)
1	143.7±2.1	143.0±1.0
2	143.7±2.5	144.3±2.1
3	145.0±2.0	145.3±1.5

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