Departamento de Hidrogeología y Química Analítica, Facultad de Ciencias Experimentales, Universidad de Almería, 04120 La Cañada de San Urbano, E-04120 Almería, Spain.
J Chromatogr A. 2010 Mar 26;1217(13):2042-9. doi: 10.1016/j.chroma.2010.01.082. Epub 2010 Feb 4.
An analytical method for the simultaneous determination of nine beta-blockers (sotalol atenolol, nadolol, pindolol, metoprolol, timolol, bisoprolol, propanolol and betaxolol) and two analgesics (paracetamol and phenazone) in river water by liquid chromatography and diode array detection is reported. The method involves a modified precolumn switching methodology replacing the small precolumn with a short C18 liquid chromatography column (50 mm x 4.6 mm, 5 microm particle size), thus allowing the preconcentration of large water sample volumes whereas interferences eluting at the first of the chromatogram were discarded to waste. This approach allowed to preconcentrate 30 mL river water samples, modified with 0.4% MeOH, achieving univariate method detection and determination limits ranged between 0.03 and 0.16 microg L(-1) and between 0.2 and 0.5 microg L(-1), respectively, with precision values lower than 9.4% for spiking levels at the quantitation limits of each analyte and lower than 4.0%, except bisoprolol (8.3%), for higher spiking levels (1.0 microg L(-1) of all analytes). Matrix background was reduced in three way data by a baseline correction following the Eilers methodology, whereas multivariate curve resolution and alternating least squares in combination with the standard addition calibration method, applied to these data, coped with overlapping peak, systematic (additive) and proportional (matrix effect) errors. The method was successfully applied for the determination of the target pharmaceuticals in river water from three places in a river stream with acceptable recoveries and precision values, taking into account the complexity of the analytical problem. The joint statistical test for the slope and the intercept of the linear regression between the nominal concentration values versus those predicted, showed that the region computed contained the theoretically expected values (0) for the intercept and (1) for the slope (at a confidence level of 95%), which indicates the absence of both constant and proportional errors in the predicted concentrations.
一种分析方法，用于同时测定九种β-受体阻滞剂（索他洛尔、阿替洛尔、纳多洛尔、吲哚洛尔、美托洛尔、噻吗洛尔、比索洛尔、普萘洛尔和倍他洛尔）和两种镇痛药（对乙酰氨基酚和非那宗）在河水中的含量，采用液相色谱和二极管阵列检测法。该方法涉及一种改良的预柱切换方法，用短的 C18 液相色谱柱（50mmx4.6mm，5μm 粒径）代替小预柱，从而允许对大体积的水样进行预浓缩，而在色谱图的第一部分洗脱的干扰物则被丢弃到废物中。这种方法允许对 30ml 河水样品进行浓缩，用 0.4%甲醇进行改性，实现了单变量方法检测和测定限分别在 0.03 到 0.16μg/L 之间和 0.2 到 0.5μg/L 之间，除了比索洛尔（8.3%）外，对于每种分析物的定量限的加标水平，精度值都低于 9.4%，对于更高的加标水平（所有分析物的 1.0μg/L），精度值都低于 4.0%。基质背景通过 Eilers 方法进行基线校正，在三向数据中降低，而多元曲线分辨率和交替最小二乘法与标准加入校准法相结合，应用于这些数据，处理重叠峰、系统（加性）和比例（基质效应）误差。该方法成功地应用于河流中三个地点的河水中目标药物的测定，回收率和精密度均令人满意，考虑到分析问题的复杂性。名义浓度值与预测值之间线性回归的斜率和截距的联合统计检验表明，计算出的区域包含了截距理论上期望的值（0）和斜率理论上期望的值（1）（置信水平为 95%），这表明预测浓度中不存在常数和比例误差。
