主题：【资料】-Limit of detection for second-order calibration methods（Doctoral Thesis）

Limit of detection for second-order calibration methods
MARÍA JOSÉ RODRÍGUEZ CUESTA
Doctoral Thesis
ROVIRA I VIRGILI UNIVERSITY
Tarragona 2006

Table of contents
Chapter 1. DESCRIPTION OF THE THESIS
1.1. Motivation  ................................................................................... -3-
1.2. Objectives .................................................................................... -4-
1.3. Structure  ..................................................................................... -6-
1.4. Notation and list of symbols ...................................................... -8-

Chapter 2. INTRODUCTION TO CHEMOMETRICS
2.1. Types of data and instruments used in Analytical Chemistry-13-
2.1.1.  Historical Background........................................................................-13-
2.1.2.  Tensor Terminology...........................................................................-14-
2.1.3.  The Concepts of Bilinearity and Trilinearity .......................................-17-
2.1.4.  Deviations from Linearity ...................................................................-20-

2.2. Calibration methods.................................................................... -22-
2.2.1.  From Zeroth- to Second-order Calibration.........................................-22-
2.2.2.  Resolution and Calibration Methods for Second-Order Data.............-27-
  2.2.2.1  Parallel Factor Analysis (PARAFAC) ...................................-31-
  2.2.2.2  Iterative Target Transformation Factor Analysis (ITTFA).....-35-
  2.2.2.3  Multivariate Curve Resolution-Alternating Least Squares
                (MCR-ALS) ..........................................................................-38-
  2.2.2.4  Multi-linear Partial Least Squares (N-PLS) ..........................-41-
2.2.3.  Uniqueness, Indeterminacies and Constraints ..................................-44-

2.3. Validation of Analytical Methods  .............................................. -50-
2.3.1.  What is Method Validation?  ..............................................................-50-
2.3.2.  Figures of Merit. International Recommendations .............................-51-
2.3.3.  Analytical Detection  ......................................................................... -55-
  2.3.3.1  Hypothesis Testing  ............................................................ -55-
  2.3.3.2  Critical Level and Detection Limit  ...................................... -56-
  2.3.3.3  Limit of Detection from Linear Calibration Curves............... -58-
  2.3.3.4  Limit of Detection in Multivariate Calibration ....................... -61-
ter 3. ESTIMATION OF THE LOD FOR PARAFAC
3.1. Introduction..................................................................................-69-
3.2. Paper.............................................................................................-73-
Determination of Carbendazim, Fuberidazole and Thiabendazole by Three-
Dimensional  Excitation–Emission Matrix  Fluorescence  and  Parallel  Factor
Analysis. Analytica Chimica Acta 491: 47-57 (2003)
Chapter 4. ESTIMATION OF THE LOD FOR ITTFA
4.1. Introduction..................................................................................-95-
4.2. Paper.............................................................................................-99-
Influence  of  Selectivity  and  Sensitivity  Parameters  on  Detection  in
Multivariate  Curve  Resolution  of  Chromatographic  Second-Order  Data.
Analytica Chimica Acta 476: 111-122 (2003)

Chapter 5. ESTIMATION OF THE LOD FOR MCR-ALS
5.1. Introduction..................................................................................-125-
5.2. Paper.............................................................................................-129-
Development  and  Validation  of  a  Method  for  Determining  Pesticides  in
Groundwater  from  Complex  Overlapped  HPLC  Signals  and  Multivariate
Curve Resolution. Chemometrics and  Intelligent Laboratory Systems 77(1-
2): 251-260 (2005)
Chapter 6. ESTIMATION OF THE LOD FOR N-PLS
6.1. Introduction ................................................................................. -157-
6.2. Paper............................................................................................. -161-
Standard Error of Prediction at Low Content Levels and Limit of Detection
Estimation for Multivariate and Multi-linear Regression. (In press)

Chapter 7. CONCLUSIONS
7.1. Introduction ................................................................................. -193-
7.2. Conclusions  ................................................................................ -193-

APPENDIX 
References ........................................................................................... -201-
Glossary and abbreviations.................................................................. -211-
List of papers and meeting contributions ............................................. -221-
Limit of detection for second-order calibration methods