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MULTIDIMENSIONAL CHROMATOGRAPHY

MULTIDIMENSIONAL CHROMATOGRAPHY. Jiří ŠEVČÍK Prague, the Czech Republic. ABOUT. UNCERTAINTY MULTI D IMENSIONALITY INFORMATION CONTENT MULTI D IMENSIONAL HW. PROBLEMS of measurements. residual error of a complex response model .

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MULTIDIMENSIONAL CHROMATOGRAPHY

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  1. MULTIDIMENSIONALCHROMATOGRAPHY Jiří ŠEVČÍK Prague, the Czech Republic MDCH-GENERAL

  2. ABOUT • UNCERTAINTY • MULTIDIMENSIONALITY • INFORMATION CONTENT • MULTIDIMENSIONAL HW MDCH-GENERAL

  3. PROBLEMS of measurements • residual error of a complex response model MDCH-GENERAL

  4. extremly high number of isomers low concentration levels missing - standards - generally valid QSPR models limited hardware possibilities PROBLEMS of measurements MDCH-GENERAL

  5. DESCRIPTORS of measurement MDCH-GENERAL

  6. what is ULTIMATE UNCERTAINTY complementarity causality ultimate uncertainty probability MDCH-GENERAL

  7. EXPRESSING UU • for one-dimensional system MDCH-GENERAL

  8. EXPRESSING UU • UU is determined by system efficiency (for one-dimensional system) MDCH-GENERAL

  9. PROBABILITY of the retention position • x position • lmean component density x MDCH-GENERAL

  10. PROBABILITY of the difference in the retention position • x0difference • asaturation factor of sep space X x0 t1 t2 MDCH-GENERAL

  11. PEAK CAPACITY • nc peak capacity • asaturation factor of sep space X x0 t1 t2 MDCH-GENERAL

  12. PEAK CAPACITYin isothermal mode • peak width = (a+btx) x0 t1 t2 MDCH-GENERAL

  13. PEAK CAPACITYin a linear temperature program mode • peak width = (a) x0 t1 t2 MDCH-GENERAL

  14. PEAK CAPACITYcomparison of operation modes MDCH-GENERAL

  15. PROBABILITY of peak overlapping • n compounds inx0 x0 t1 t2 MDCH-GENERAL

  16. PROBABILITY of peak clusters overlapping • pn number of clusters with the same number of compounds x0 t1 t2 MDCH-GENERAL

  17. CLUSTERS (n-tets) in one-dimensional chromatography MDCH-GENERAL

  18. WHAT isthe chromatographicdimension • chromatography (a constant value of KD) • switching (a straight inlet-separation-detector) MDCH-GENERAL

  19. WHAT ismultidimensional • chromatography (within one run changes of KD for the same analyte) • switching (within one run multiplication of any part of trajectory inlet-separation-detector) MDCH-GENERAL

  20. WHAT ishyphenation • can be multi-d-chromatography (HPLC-GC) • can be multi-d-switching (FID-MS) • interface of different techniques MDCH-GENERAL

  21. PEAK CLUSTERS in multidimesional chromatography • pn number of clusters with the same number of compounds KD3 KD2 KD1 MDCH-GENERAL

  22. PEAK CAPACITY in multidimesional chromatography • nc(d) maximum number of separated peaks KD3 KD2 KD1 MDCH-GENERAL

  23. RELATIVE PEAK DENSITY in multidimensional chromatography MDCH-GENERAL

  24. WHAT isthe information content • uncertainty (entropy) prior to an experiment and after it • probability that some input and output events will happen MDCH-GENERAL

  25. WHAT isthe information content • input P(Ii) prior to an experiment - there is an analyte i • output P(Ok) after the experiment – there will be a measurable signal (larger than LOD) • conditional probability MDCH-GENERAL

  26. CONDITIONAL PROBABILITIES • P(Ok/Ii) there will be the output - measurable signal larger than LOD when there will be the analyte i as the input • P(Ii/Ok) there will be the analyte i as the input when there will be the output - measurable signal larger than LOD MDCH-GENERAL

  27. PROBABILITIES in chromatography output/input relation aposteriory probability output prob m k 1 P(Ok/Ii) P(Ii/Ok) m k 1 P(Ok) apriori probability 1 i n 1 1 P(Ii) 1 i n MDCH-GENERAL

  28. UNCERTAINTY (ENTROPY) of • a priori status H(I) prior to an analysis • a posteriori status H(I/Ok) after the signal Ok has been measured • a posteriori status H(I/O) after the analysis has been performed MDCH-GENERAL

  29. UNCERTAINTY (ENTROPY) of • a priori status H(I) prior to an analysis MDCH-GENERAL

  30. UNCERTAINTY (ENTROPY) of a posteriori status H(I/Ok) after the signal Ok has been measured MDCH-GENERAL

  31. UNCERTAINTY (ENTROPY) of • a posteriori status H(I/O) after the analysis has been performed MDCH-GENERAL

  32. INFORMATION CONTENT • the difference between uncertainties before and after the analysis has been carried out multidimensional MDCH-GENERAL

  33. INFORMATION CONTENTways of quantification • integration • assumption of the normal distribution of the data and of the measuring error • a histogram • an approach based on maximum peak capacity • an approach based on real peak capacity MDCH-GENERAL

  34. QUANTIFICATIONusing peak capacity • separation system configuration(efficiency, selectivity, operational modes) • sample composition(number of compounds, chromatographic similiarities and overlap) MDCH-GENERAL

  35. INFORMATION CONTENTin multidimensional chromatography MDCH-GENERAL

  36. INFORMATION based GC INSTRUMENTATION • multidimensional column systems IF (RIA)i= a THEN (RIA)k= c AND (RIA)k= d • hyphenated techniques P(SA)k <<>> P(SB)k • expert systems lim Σ(ε)i= 0 MDCH-GENERAL

  37. multidimensional chromatographySYSTEMS serial parallel KD1 <> KD2 <> KDd MDCH-GENERAL

  38. multidimensional chromatographySERIAL SYSTEMS recycle comprehensive tandem MDCH-GENERAL

  39. SWITCHING MODESin multidimensional chromatography MDCH-GENERAL

  40. PROCESS OF IDENTIFICATION • matching actual found pattern with true one - peak identification (noise reduction, integration, deconvolution) - peak correlation (similarity link) - analyte identification (match with standards) • redundant information content MDCH-GENERAL

  41. MS-SIM separation of GC non separated isomers MDCH-GENERAL

  42. FUTURE INSTRUMENTATION • principle of additivity of partial probabilities MDCH-GENERAL

  43. FUTURE INSTRUMENTATION • HW miniaturization • SW deconvolution routines multidimensional statistics MDCH-GENERAL

  44. ABOUT • UNCERTAINTY • MULTIDIMENSIONALITY • INFORMATION CONTENT • MULTIDIMENSIONAL HW MDCH-GENERAL

  45. . MULTIDIMENSIONAL chromatography is the analytical approach to the Bohr principle of complementarity. MDCH-GENERAL

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