multidimensional chromatography
DESCRIPTION
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 . - PowerPoint PPT PresentationTRANSCRIPT
020213GK MDCH-GENERAL
MULTIDIMENSIONAL
CHROMATOGRAPHY
Jiří ŠEVČÍKPrague, the Czech Republic
020213GK MDCH-GENERAL
ABOUT
UNCERTAINTY
MULTIDIMENSIONALITY
INFORMATION CONTENT
MULTIDIMENSIONAL HW
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PROBLEMS of measurements
residual error of a complex response model
n
iii XbaY1
)(
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PROBLEMS of measurements
extremly high number of isomers
low concentration levels
missing - standards - generally valid QSPR models
limited hardware possibilities
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DESCRIPTORS of measurement
residua l error o f response m odel
sta nda rds
Q SP R m odels
ha rdw a re
L I M I T E D B Y
reproducib ility
identif ica tion
inform a tion ba sed instrum enta tion
inform a tion content
a dd itivity of p roba bility
ultim a te uncerta inty
Q U A N T I F I E D B Y
M EASUREM ENT
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what is ULTIMATE UNCERTAINTY
causality
ultimate uncertainty
complementarity
probability
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EXPRESSING UU
for one-dimensional system NZPUU nn /11
nrr
Rij
ijij
141
ijij
ijn Rr
rZUU 11
41
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EXPRESSING UU
UU is determined by system efficiency (for one-dimensional system)
ttt ij // nttw ij /14 /
nttttZUU
i
in 122 /
/
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PROBABILITY of the retention position
x position mean component density
xexP
x
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PROBABILITY of the difference in the retention position
x0 difference saturation factor of sep space X
eedxexxP xx
x 11 00
00
x0
t1 t2
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PEAK CAPACITY
nc peak capacity saturation factor of sep space X
x0
t1 t2
mn
mXxx
c
100
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PEAK CAPACITYin isothermal mode
peak width = (a+btx)
x0
t1 t2
1
2ln1114
12
1tbatba
RbdttR
nnt
tc
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PEAK CAPACITYin a linear temperature program mode
peak width = (a)
x0
t1 t2
1211111
2
1
ttRw
dtwR
nt
tc
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PEAK CAPACITYcomparison of operation modes
The effect of the chromatografic conditions on the peak capacity in a one-dimensional system
(for R=1 and k<1;10>)
0
500
1 000
0 80 000 160 000
plate number
peak
cap
acity
isothermal temp.program
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PROBABILITY of peak overlapping
n compounds in x0
x0
t1 t2
12 1 n
n eeP
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PROBABILITY of peak clusters overlapping
pn number of clusters with the same number of compounds
x0
t1 t2
nn Pmp
emeempn
n 1
2 1
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CLUSTERS (n-tets) in one-dimensional chromatography
1000
0
2000
0
3000
0
4000
0
5000
0
6000
0
7000
0
8000
0
9000
0
1000
0010
9
8
76
54
32
1
0
5
10
15
20
25
30
35
Poče
t sin
glet
ů v
n-te
tech
Počet teoretických pater
n-tet
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WHAT isthe chromatographic
dimension
chromatography (a constant value of KD)
switching (a straight inlet-separation-detector)
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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)
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WHAT ishyphenation
can be multi-d-chromatography (HPLC-GC)
can be multi-d-switching (FID-MS)
interface of different techniques
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PEAK CLUSTERS in multidimesional chromatography
pn number of clusters with the same number of compounds
KD1
122 1
nd
n dd
dd
eenmp
d
d
dd
e
emp ddd
2
2
12
KD2
KD3
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PEAK CAPACITY in multidimesional chromatography
nc(d) maximum number of separated peaks
KD1
KD2
KD3
d
icd
dd
c indn
121
22
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RELATIVE PEAK DENSITY in multidimensional chromatography
0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1
0 1 2 3 4 5 6 7
log(m)
p/m
1-D 2-D 3-D 4-D
_
_
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WHAT isthe information content
uncertainty (entropy) prior to an experiment
and after it
probability that some input and output events will happen
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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
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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
i
kikm
kkik
kikik IP
OIPOP
OIPOP
OIPOPIOP /
/
//
1
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PROBABILITIES in chromatography
output/input relation
P(Ok/Ii)
P(Ii/Ok)
P(Ok)
m k 1
aposteriory probability
m k 1
1 i n
1 i n11
output prob
P(Ii)
apriori probability
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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
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UNCERTAINTY (ENTROPY) of
a priori status H(I)prior to an analysis
in
ii IPldIPIH
1
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UNCERTAINTY (ENTROPY) of
a posteriori status H(I/Ok)after the signal Ok has been measured
kin
ikik OIPldOIPOIH ///
1
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UNCERTAINTY (ENTROPY) of
a posteriori status H(I/O)after the analysis has been performed
km
kk OIHOPOIH //
1
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INFORMATION CONTENT
the difference between uncertaintiesbefore and after the analysis has been carried out
dIOIIIId
dd
//
1
OIHIHOII //
multidimensional
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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
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QUANTIFICATIONusing peak capacity
separation system configuration (efficiency, selectivity, operational modes) sample composition (number of compounds, chromatographic similiarities and overlap)
nR
tt
ldnldI1log
logmin
max
max
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INFORMATION CONTENTin multidimensional chromatography
mode expression [bit]
IXFR 3 to 8
IMON 5 to 11
2
122
2
22
2
1
11 100
1141 RI
AAn
AAnld
XFRIAAnld
1
11
141
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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
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multidimensional chromatographySYSTEMS
serialparallel
KD1 <> KD2 <> KDd
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multidimensional chromatographySERIAL SYSTEMS
recycle comprehensive
tandem
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SWITCHING MODESin multidimensional chromatography
SFL solvent-flushXFR transferMON monitoringBFL back-flushTRP trappingRJN re-injecton
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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
ii
mii S
APSPAP1
1
reqobt
SISI
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MS-SIM separation of GC non separated isomers
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FUTURE INSTRUMENTATION
principle of additivity of partial probabilities
1lim1
iiP
),,( 2iji rPifUU
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FUTURE INSTRUMENTATION
HW miniaturization
SW deconvolution routines multidimensional statistics
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ABOUT
UNCERTAINTY
MULTIDIMENSIONALITY
INFORMATION CONTENT
MULTIDIMENSIONAL HW
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MULTIDIMENSIONALchromatography
is the analytical approach to
the Bohr principle of complementarity.
.