020213GKMDCH-GENERAL MULTIDIMENSIONAL CHROMATOGRAPHY Jiří ŠEVČÍK Prague, the Czech Republic

020213GKMDCH-GENERAL ABOUT UNCERTAINTY MULTIDIMENSIONALITY INFORMATION CONTENT MULTIDIMENSIONAL HW

020213GKMDCH-GENERAL PROBLEMS of measurements residual error of a complex response model

020213GKMDCH-GENERAL PROBLEMS of measurements extremly high number of isomers low concentration levels missing - standards - generally valid QSPR models limited hardware possibilities

020213GKMDCH-GENERAL DESCRIPTORS of measurement

020213GKMDCH-GENERAL what is ULTIMATE UNCERTAINTY causality ultimate uncertainty complementarity probability

020213GKMDCH-GENERAL EXPRESSING UU for one-dimensional system

020213GKMDCH-GENERAL EXPRESSING UU UU is determined by system efficiency (for one-dimensional system)

020213GKMDCH-GENERAL PROBABILITY of the retention position x position mean component density x

020213GKMDCH-GENERAL PROBABILITY of the difference in the retention position x 0 difference  saturation factor of sep space X x0x0 t 1 t 2

020213GKMDCH-GENERAL PEAK CAPACITY n c peak capacity  saturation factor of sep space X x0x0 t 1 t 2

020213GKMDCH-GENERAL PEAK CAPACITY in isothermal mode peak width = (a+bt x ) x0x0 t 1 t 2

020213GKMDCH-GENERAL PEAK CAPACITY in a linear temperature program mode peak width = (a) x0x0 t 1 t 2

020213GKMDCH-GENERAL PEAK CAPACITY comparison of operation modes

020213GKMDCH-GENERAL PROBABILITY of peak overlapping n compounds in x 0 x0x0 t 1 t 2

020213GKMDCH-GENERAL PROBABILITY of peak clusters overlapping p n number of clusters with the same number of compounds x0x0 t 1 t 2

020213GKMDCH-GENERAL CLUSTERS (n-tets) in one-dimensional chromatography

020213GKMDCH-GENERAL WHAT is the chromatographic dimension chromatography ( a constant value of K D ) switching ( a straight inlet-separation-detector )

020213GKMDCH-GENERAL WHAT is multidimensional chromatography ( within one run changes of K D for the same analyte ) switching ( within one run multiplication of any part of trajectory inlet-separation-detector )

020213GKMDCH-GENERAL WHAT is hyphenation can be multi-d-chromatography ( HPLC-GC ) can be multi-d-switching ( FID-MS ) interface of different techniques

020213GKMDCH-GENERAL PEAK CLUSTERS in multidimesional chromatography p n number of clusters with the same number of compounds K D1 K D2 K D3

020213GKMDCH-GENERAL PEAK CAPACITY in multidimesional chromatography n c (d) maximum number of separated peaks K D1 K D2 K D3

020213GKMDCH-GENERAL RELATIVE PEAK DENSITY in multidimensional chromatography

020213GKMDCH-GENERAL WHAT is the information content uncertainty (entropy) prior to an experiment and after it probability that some input and output events will happen

020213GKMDCH-GENERAL WHAT is the information content input P(I i ) prior to an experiment - there is an analyte i output P(O k ) after the experiment – there will be a measurable signal (larger than LOD) conditional probability

020213GKMDCH-GENERAL CONDITIONAL PROBABILITIES P(O k /I i ) there will be the output - measurable signal larger than LOD when there will be the analyte i as the input P(I i /O k ) there will be the analyte i as the input when there will be the output - measurable signal larger than LOD

020213GKMDCH-GENERAL PROBABILITIES in chromatography output/input relation P(O k /I i ) P(I i /O k ) P(O k ) m k 1 m k 1 aposteriory probability m k 1m k 1 1 i n 1 1 output prob P(I i ) apriori probability

020213GKMDCH-GENERAL UNCERTAINTY (ENTROPY) of a priori status H(I) prior to an analysis a posteriori status H(I/O k ) after the signal O k has been measured a posteriori status H(I/O) after the analysis has been performed

020213GKMDCH-GENERAL UNCERTAINTY (ENTROPY) of a priori status H(I) prior to an analysis

020213GKMDCH-GENERAL UNCERTAINTY (ENTROPY) of a posteriori status H(I/O k ) after the signal O k has been measured

020213GKMDCH-GENERAL UNCERTAINTY (ENTROPY) of a posteriori status H(I/O) after the analysis has been performed

020213GKMDCH-GENERAL INFORMATION CONTENT the difference between uncertainties before and after the analysis has been carried out multidimensional

020213GKMDCH-GENERAL INFORMATION CONTENT ways 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

020213GKMDCH-GENERAL QUANTIFICATION using peak capacity separation system configuration (efficiency, selectivity, operational modes) sample composition (number of compounds, chromatographic similiarities and overlap)

020213GKMDCH-GENERAL INFORMATION CONTENT in multidimensional chromatography mode expression [bit] I XFR 3 to 8 I MON 5 to 11

020213GKMDCH-GENERAL INFORMATION based GC INSTRUMENTATION multidimensional column systems IF (RI A ) i = a THEN (RI A ) k = c AND (RI A ) k = d hyphenated techniques P(S A ) k > P(S B ) k expert systems lim Σ ( ε ) i = 0

020213GKMDCH-GENERAL multidimensional chromatography SYSTEMS serial parallel K D1 <> K D2 <> K Dd

020213GKMDCH-GENERAL multidimensional chromatography SERIAL SYSTEMS recyclecomprehensive tandem

020213GKMDCH-GENERAL SWITCHING MODES in multidimensional chromatography SFLsolvent-flush XFRtransfer MONmonitoring BFLback-flush TRPtrapping RJNre-injecton

020213GKMDCH-GENERAL 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

020213GKMDCH-GENERAL MS-SIM separation of GC non separated isomers

020213GKMDCH-GENERAL FUTURE INSTRUMENTATION principle of additivity of partial probabilities

020213GKMDCH-GENERAL FUTURE INSTRUMENTATION HW miniaturization SW deconvolution routines multidimensional statistics

020213GKMDCH-GENERAL ABOUT UNCERTAINTY MULTIDIMENSIONALITY INFORMATION CONTENT MULTIDIMENSIONAL HW

020213GKMDCH-GENERAL MULTIDIMENSIONAL chromatography is the analytical approach to the Bohr principle of complementarity..