Faculty of Chemistry, Razi University, Kermanshah 671496734, Iran.
Faculty of Chemistry, Razi University, Kermanshah 671496734, Iran; Laboratorio de Desarrollo Analítico y Quimiometría (LADAQ), Cátedra de Química Analítica I, Universidad Nacional del Litoral, Ciudad Universitaria, CC 242 (S3000ZAA) Santa Fe, Argentina.
Talanta. 2015 Jan;131:26-37. doi: 10.1016/j.talanta.2014.07.053. Epub 2014 Jul 26.
For the first time, an analytical methodology based on differential pulse voltammetry (DPV) at a glassy carbon electrode (GCE) and integration of three efficient strategies including variable selection based on ant colony optimization (ACO), mathematical pre-processing selection by genetic algorithm (GA), and sample selection (SS) through a distance-based procedure to improve partial least squares-1 (PLS-1, ACO-GA-SS-PLS-1) multivariate calibration (MVC) for the simultaneous determination of five opium alkaloids including morphine (MOP), noscapine (NOP), thebaine (TEB), codeine (COD), and papaverine (PAP) was used and validated. The baselines of the DPV signals were modeled as a smooth curve, using P-splines, a combination of B-splines and a discrete roughness penalty. After subtraction of the baseline we got a signal with a two-component probability density. One component was for the peaks and it was approximated by a uniform distribution on the potential axis. The other component was for the observed noise around the baseline. Some sources of bi-linearity deviation for electrochemical data were discussed and analyzed. The lack of bi-linearity was tackled by potential shift correction using correlation optimized warping (COW) algorithm. The MVC model was developed as a quinternary calibration model in a blank human serum sample (drug-free) provided by a healthy volunteer to regard the presence of a strong matrix effect which may be caused by the possible interferents present in the serum, and it was validated and tested with two independent sets of analytes mixtures in the blank and actual human serum samples, respectively. Fortunately, the proposed methodology was successful in simultaneous determination of MOP, NOP, TEB, COD, and PAP in both blank and actual human serum samples and its results were satisfactory comparable to those obtained by applying the reference method based on high performance liquid chromatography-ultraviolet detection (HPLC-UV).
首次在玻碳电极（GCE）上基于差分脉冲伏安法（DPV）并集成三种有效策略，包括基于蚁群优化（ACO）的变量选择、基于遗传算法（GA）的数学预处理选择和基于距离的样品选择（SS），建立一种分析方法，用于同时测定五种鸦片生物碱，包括吗啡（MOP）、那可丁（NOP）、蒂巴因（TEB）、可待因（COD）和罂粟碱（PAP）。DPV 信号的基线采用 P 样条（一种 B 样条和离散粗糙度惩罚的组合）建模为平滑曲线。扣除基线后，我们得到了一个具有双组分概率密度的信号。一个分量是用于峰，它在电位轴上近似为均匀分布。另一个分量是用于观察基线周围的噪声。讨论并分析了电化学数据的双线性偏差的一些来源。通过使用相关优化扭曲（COW）算法进行电位偏移校正来解决双线性不足的问题。该方法建立了一个五元校准模型，用于一个健康志愿者提供的空白人血清样本（无药物），以考虑到可能存在由血清中可能存在的干扰物引起的强烈基质效应，并分别在空白和实际人血清样本中使用两个独立的分析物混合物集进行验证和测试。幸运的是，该方法成功地用于同时测定空白和实际人血清样本中的 MOP、NOP、TEB、COD 和 PAP，其结果与基于高效液相色谱-紫外检测（HPLC-UV）的参考方法获得的结果相当满意。
