目的:建立HPLC-CAD方法同时测定知母中芒果苷和知母皂苷BⅡ的含量.方法:采用Acclaim-C18色谱柱(150 mm × 4.6 mm,3 μm),以乙腈(A )-0.2％醋酸水溶液(B)为流动相,梯度洗脱(0～10 min,15％A → 21％A;10～12 min,21％A → 23％A,12～30 min,23％A → 25％A ),流速 1.0 mL · min-1,柱温30 ℃;电雾式检测器(CAD)参数:采集频率10 Hz,雾化温度55℃,滤波为5 s.结果:知母中芒果苷和知母皂苷BⅡ均具有良好的线性关系(r＞0.999 ),LOD分别为0.43 ng和1.20 ng,LOQ分别为1.28 ng和4.80 ng,精密度、重复性、24 h稳定性试验的RSD均小于3.0％,平均加样回收率分别为102.3％和95.2％.11批样品中芒果苷和知母皂苷B Ⅱ的含量范围分别为0.54％～1.69％和3.27％～5.57％.结论:建立的HPLC-CAD法可同时对知母中芒果苷和知母皂苷B Ⅱ进行含量测定,为知母药材和饮片的检测分析和质量控制提供了新的方法.

Objective To develop a method for the determination of five furostanol saponins(timosaponin N,timosaponin L, timosaponin BⅡ,25R-timosaponin BⅡ,and 25S-officinalisnin-Ⅰ)in rhizome and fibrous root of Anemarrhena asphodeloides Bge. by HPLC with the charged aerosol detector(CAD). Methods The analysis was performed on TechMate C18-ST-II(250 mm×4.6 mm,5μm)with acetonitrile:water(22:78,V/V),the flow rate of 1.0 ml/min and column temperature at 30℃. The Corona parameters were as follows:sampling rate 10 Hz,filter 5 s,and the nebulizer temperature 55℃. Results The approach showed good linearity for five saponins. The correlation coefficients(r2)for calibration curves varied from 0.9992 to 0.9998. The limits of detection(LOD)were 0.28,0.92,0.92,0.92 and 0.92 ng for five steroidal saponins,respectively. The limits of quantitation(LOQ)were found to be 0.92, 2.77,2.77,2.77 and 2.76 ng,respectively. RSD calculated from peak area of precision,repeatability and stability in 48 h were all less than 3.0%. The average recoveries of timosaponin N,timosaponin L,timosaponin BⅡ,25R-timosaponinBⅡ,and 25S-officinalis-nin-Ⅰwere 98.17%,101.37%,98.53%,97.63%,and 98.17%,respectively. Conclusion The developed method is accurate,reli-able,which could be applied to the quality control of multiple components in A. asphodeloides Bge.

目的:采用超高效液相色谱-飞行时间质谱(UPLC-Q-TOF-MSE)表征并快速在线鉴定麦冬中甾体皂苷类成分;结合呋甾皂苷在反向色谱上的保留规律,鉴别同分异构体.方法:运用2种反相色谱柱(ACQUITY UPLC HSS T3和Agela VenusilXBP C18-2),在2种溶剂系统(0.1％甲酸/水-0.1％甲酸/乙腈,丙酮-水)和3个洗脱条件下对系列呋甾皂苷的色谱保留规律进行总结.利用UPLC-Q-TOF-MSE对麦冬成分进行分析,获得质谱数据.结果:3种色谱条件下呋甾皂苷的相对保留时间一致,呈现如下保留规律:甾体皂苷中糖链结构相同,苷元上羟基的数目越多保留时间越短;仅羟基位置不同时,保留时间为1位羟基＜17位羟基＜14位羟基;仅C-26位糖链糖基连接位置不同时,葡萄糖-(1→6)-葡萄糖＜葡萄糖-(1→2)-葡萄糖;从麦冬表征的图谱中共鉴定了21个色谱峰,其中14个呋甾皂苷,7个为螺甾皂苷.结论:色谱保留时间能为呋甾皂苷同分异构体的液质联用在线鉴定提供有益的数据支持.

In this work, a simple and rapid high-performance liquid chromatography coupled with charged aerosol detector (HPLC-CAD) method was first developed for the quantitation of toosendanin, the major constituent of the dried fruit of Melia toosendan Sieb. Et Zucc. Samples were well separated on an Agilent ZOBAX SB C18 column (4.6 mm × 250 mm, 5 μm) by isocratic elution using 33 % acetonitrile and 67 % water containing 0.1 % formic acid (v/v) at the flow rate of 1.0 mL min−1. The nitrogen inlet pressure of the charged aerosol detector (CAD) was 35 psi, and the nebulizer chamber temperature was 35 °C. The established method was well validated. Satisfactory linearity was achieved (r 2 > 0.9997) in a relatively wide concentration range (5–500 μg mL−1). The intra- and inter-day precisions, repeatability, and stability of the method were good with relative standard deviations (RSDs) of 1.05, 2.23, 2.39, and 2.03 %, respectively. The method also showed excellent accuracy with recovery rates of 97.42–101.87 %. Particularly, CAD showed much better sensitivity (LOQ 4 μg mL−1) than evaporative light scattering detector (LOQ 100 μg mL−1) for toosendanin’s determination. The established method was further applied in the quantitation of toosendanin in 39 batches of raw and stir-fried toosendan fructus. The HPLC-CAD method was rapid and accurate, and could be used for the routine analysis and quality control of toosendan fructus and its preparations.

探讨沈阳科创化学品有限公司生产的30%氯氟吡氧乙酸异辛酯·辛酰溴苯腈·烟嘧磺隆可分散油悬浮剂在玉米田上除草效果及对玉米安全性,2013、2014年黑龙江省七星泡农场进行了试验,现将试验情况总结如下。1试验材料与方法供试药剂:30%氯氟吡氧乙酸异辛酯·辛酰溴苯腈·烟嘧磺隆可分散油悬浮剂由沈阳科创化学品有限公