Peak Modeling Approach to Accurate Assignment of First-Dimension Retention Times in Comprehensive Two-Dimensional Chromatography
Peak Modeling Approach to Accurate Assignment of First-Dimension Retention Times in Comprehensive Two-Dimensional Chromatography
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DOI：
10.1021/ac900960n
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发表时间：
2009-08-15
影响因子：
7.4
通讯作者：
Marriott, Philip J.
中科院分区：
文献类型：
--
作者：
Adcock, Jacqui L.;Adams, Mike;Marriott, Philip J.
基于调制相位和周期的峰的第一维度保留的建模允许可靠地预测在全面的二维色谱实验中生成的调制峰分布。通过应用逆过程，还可以使用调制峰的轮廓（其高度或面积）来预测主柱尺寸的原始输入色谱带的形状和参数（保留时间、标准偏差、面积）。这允许准确推导第一维保留时间（RSD 0.02%），其等于非调制实验的保留时间，而不是依赖于调制过程产生的主要调制峰的保留时间（RSD 0.16%）。后一种度量可以产生至少相差实验中采用的调制周期的保留时间，这在180度异相调制的点处显示保留时间对调制相位图的不连续性。相反，这里提出的新过程给出了基本上与调制相位和周期无关的结果。这允许将准确值分配给第一尺寸保持。所提出的度量占的时间上的第二维度，相位的分布，和保持时间，采样的溶质被保留在调制接口。该方法还可以基于最大的三个调制峰值，而不是所有调制峰值。这简化了分配保留时间的任务，并且带标准偏差或保留时间的精度损失很小，前提是这些峰在第一或第二维中不全部过载。
Modeling of first-dimension retention of peaks based on modulation phase and period allows reliable prediction of the modulated peak distributions generated in the comprehensive two-dimensional chromatography experiment. By application of the inverse process, it is also possible to use the profile of the modulated peaks (their heights or areas) to predict the shape and parameters of the original input chromatographic band (retention time, standard deviation, area) for the primary column dimension. This allows an accurate derivation of the first-dimension retention time (RSD 0.02%) which is equal to that for the non-modulated experiment, rather than relying upon the retention time of the major modulated peak generated by the modulation process (RSD 0.16%). The latter metric can produce a retention time that differs by at least the modulation period employed in the experiment, which displays a discontinuity in the retention time vs modulation phase plot at the point of the 180 degrees out-of-phase modulation. In contrast, the new procedure proposed here gives a result that is essentially independent of modulation phase and period). This permits an accurate value to be assigned to the first-dimension retention. The proposed metric accounts for the time on the second-dimension, the phase of the distribution, and the hold-up time that the sampled solute is retained in the modulating interface. The approach may also be based on the largest three modulated peaks, rather than all modulated peaks. This simplifies the task of assigning the retention time with little loss of precision in band standard deviation or retention time, provided that these peaks are not all overloaded in the first or second dimension.