Although IUPAC has recommended a probabilistic approach to determining limit of detection (LOD) based on false-positive and false-negative rates for more than 20 years, the LOD definition for ion-selective electrodes (ISEs) long predates these recommendations and conflicts substantively with them. Although it is well known that the ISE LOD definition does not follow best practice, it continues to be used due to simplicity and a lack of available methods for estimating LOD for nonlinear sensors. Here, we use ISEs as a model system for estimation of LOD for nonlinear sensors that is consistent with broad IUPAC recommendations and justified using statistical theory. Using freely available software, the new approach and updated definition is demonstrated through theory, simulation, and an environmental application. The results show that the current LOD definition for ISEs performs substantially worse than the proposed definition when assessed against IUPAC recommendations, including ignoring sensor noise and LOD uncertainty, leading to bias of an order of magnitude or more. Further, the environmental application shows that the new definition, which includes estimates of LOD uncertainty, allows more objective assessment of sensor response and fitness for purpose. The growing demand for ultrasensitive sensors that operate in complex matrices has pushed the boundaries of traditional calibration approaches. These sensors often operate near their limit of detection (LOD), with additional challenges created if their response is nonlinear. These challenges are amplified when assessing new sensors, since they may be less reproducible and noisier than benchmark techniques.

中文翻译：

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为离子选择电极和其他非线性传感器建立有意义的检测限。

尽管IUPAC已建议使用基于概率为20％的基于假阳性和假阴性率的检测限（LOD）的概率方法，但离子选择电极（ISE）的LOD定义早于这些建议，并且与他们。尽管众所周知，ISE LOD定义未遵循最佳实践，但由于其简单性和缺乏估算非线性传感器LOD的可用方法，因此仍在继续使用它。在这里，我们使用ISE作为模型系统来估计非线性传感器的LOD，这与广泛的IUPAC建议是一致的，并且使用统计理论是合理的。使用免费提供的软件，通过理论，模拟和环境应用论证了新方法和更新的定义。结果表明，当根据IUPAC建议进行评估时，当前ISE的LOD定义的性能要比拟议的定义差很多，包括忽略传感器噪声和LOD不确定性，从而导致一个数量级或更大的偏差。此外，环境应用表明，新的定义（包括LOD不确定性的估计）允许对传感器响应和用途的适应性进行更客观的评估。对在复杂矩阵中运行的超灵敏传感器的需求不断增长，这已经突破了传统校准方法的界限。这些传感器通常在其检测极限（LOD）附近工作，如果它们的响应是非线性的，则会带来其他挑战。在评估新传感器时，这些挑战会更加严重，