Generalized Rank Annihilation Factor Analysis Anal Chem 58(1986)496. E Sanchez B R Kowalski.
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Transcript of Generalized Rank Annihilation Factor Analysis Anal Chem 58(1986)496. E Sanchez B R Kowalski.
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Generalized Rank Annihilation Factor Analysis
Anal Chem 58(1986)496.E Sanchez B R Kowalski
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Bilinear data
2
1
3
2 .1 .2 .3 .2
e(Excit.)
f(Emiss.)
X1 (Fluoresc.)
=
One component Rank =1
Conc.
0.4 0.8 1.2 0.8
0.2 0.4 0.6 0.4
0.6 1.2 1.8 1.2
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2 1
1 2
3 1
1 0
0 3
.1 .2 .3 .2
.2 .4 .4 .3
21.1+13.2
21.1+13.2
11.1+23.2
31.2+13.3
Two components
E FConc.
=
X2 (Fluoresc.)
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0.2 +0.6 0.4 +1.2 0.6 +1.2 0.4 + .9
0.1 +1.2 0.2 +2.4 0.3 +2.4 0.2 +1.8
0.3 +0.6 0.6 +1.2 0.9 +1.2 0.6 +0.9
Two components
X2 =
Rank = 2
0.4 0.8 1.2 0.8
0.2 0.4 0.6 0.4
0.6 1.2 1.8 1.2
one component (calibration matrix)
Rank = 1
X1 =
Lorber, 1984 X2- 0.5 X1 = ERank=2 Rank=1
Quantification of one component.
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0.2 +0.6 0.4 +1.2 0.6 +1.2 0.4 +0.9
0.1 +1.2 0.2 +2.4 0.3 +2.4 0.2 +1.8
0.3 +0.6 0.6 +1.2 0.9 +1.2 0.6 +0.9
Two components(sample)
X2 =
Rank = 2
0.4+0.2 0.8+0.4 1.2+0.4 0.8+0.3
0.2+0.4 0.4+0.8 0.6+0.8 0.4+0.6
0.6+0.2 1.2+0.4 1.8+0.4 1.2+0.3
Two components(calibration)
Rank = 2
X3 =
What about quantific. of more than one component?
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Generalized RAFA [Anal Chem 1986, 58, 496-499. B.R. Kowalski]
1. Non-iterative [Lorber, 1984].
2. Simultaneous detn. of analytes using
Just one bilinear calibration spectrum
from one mixture of standards.
a. Bilinear spectrum of each analyte
b. Relative conc.s
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Theory
E FT = X2
E FT = X1
sample :
Calibration :
E = X2(FT)+ -1
E = X1(FT)+ -1
X1(FT)+ -1 = X2(FT)+ -1
X1 Z = U S VT Z -1
Z = V S-1 Z* (definition)
Common F and E
Trilinearity
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X1 V S-1 Z* = U S VT V S-1 Z* -1
I
I
UT X1 V S-1 Z* = Z* -1
R V = V (eigenvector analysis)
FT = (V S-1 Z*)+
E = U Z* -1
-1 =
?
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Simult. detn. of two acids in a sample
H2A HA A
H2B HB B
using pH-metric titration
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H2A HA A
H2B HB Asample
C0A ?
C0B ?
H2A HA A
H2B HB Acalibr.
C0A =0.02 M
C0B =0.04 M
Data matrices
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sample
calibration
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Only HA-
and HB- are optically active.
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sample
calibration
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[Zstar,λ]=eig(Usm‘ * Xcl‘ * Vsm* inv(Ssm))
[Usm,Ssm,Vsm] = svd(Xsm')
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0.6669
1.9998
λ=
(CoA)cl
(CoA)sm
(CoB)cl
(CoB)sm
, (CoA)cl=0.02 M
=> (CoA)sm=0.03 M
, (CoB)cl=0.04 M
=> (CoB)sm=0.02 M
0.03
0.02
β =
15
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F = pinv( Vsm * inv( Ssm ) * Zstar)
Conc. profiles
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E = Usm * Zstar * inv(β)
spectral profiles
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What if:
The calibration sample includes some components that are not present in unknown sample,
And there be some components in unknown sample not present in the calibration sample.
HPLC-DAD chromatogram for A,B, and C (as CL),
for ?,?,and ? (as SM)
Example:The General C
ondition
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Xcl
CAcl= 1 mM
CBcl= 3 mM
CCcl= 2 mM
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Xsm
?, ?, and ?, ..
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[Zstar,λ]=eig(Utot‘ * Xsm‘ * Vtot* inv(Stot))
[Utot,Stot,Vtot] = svd(Xtot')
Xtot = Xcl + Xsm The total space, rank =4
(includes A, B, C ,and D)
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0.9999 0 0 0
0 0.0003 0 0
0 0 0.5000 0
0 0 0 0.3334
λ= β / ( β + ξ )
C?sm
C?sm+C?cl=0.9999 0.0003 0.5000 0.3334
C?cl=0
Only in sm
C?sm=0
Only in cl
C?sm= C?cl
2C?sm= C?clC
BAD
CBsm= 3 mM
CCsm= 1 mM
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F = pinv( Vtot * inv( Stot ) * Zstar)
Conc. profiles
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E = Utot * Zstar
spectral profiles
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Non-bilinear RA
Analyte detn.
..in the presence of unaccounted spectral interference..
Rank for the pure component >1
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H2A HA A
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One compon, but Rank=…3
Xcl
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H2A and H2B
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Rank(Xsm)=5H2A and H2B
Interference
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Conc. Prof.s
Spect. Prof.s
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0.9415 0 0 0 0
0 0.0003 0 0 0
0 0 -0.003 0 0
0 0 0 2.0044 0
0 0 0 0 2.0010
λ of H2B
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DirectExponentialCurveResolutionAlgorithm
J. Chemom. 14 (2000) 213-227.
DECRA
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Model base: an exponential decay
162
54
18
6
2
162
54
18
6
2
x2 x1
162/54=
54/18=
18/6=
6/2=
3
3
3
3
shift
x
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C1 = e –k t
C2 = e –k (t+S)
C1
C2 ===e –kt +k(t+S)= e –k S
e –k t
e –k (t+S)
k = ln() / S
x2 :
x1 :
Shift
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Shift=7
x2
x1
1st Ord Data
From 1 sample
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k = ln() / 7
=0.1
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cP
sPT
cQ
sQT
cR
sRT
= + +
XExpon.Decay
2st Ord Data
From 1 sample
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Trilinear structureN
X1
X2
= +
E
Gives k1 and k2X
2-way
(MN)
X
3-way
((M-S) N 2)
Stacking
E
F
λ
1
M-S
1+S
M
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Decomposition of a number of colorants to colorless products..
A A’
B B’
C C’
…
1st order reactions
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svd(X)=
6279.5
294.0
34.4
0.7
0.6
0.6
…
Three components
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Shift = 10 min
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Estimated F
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estmated E
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k = ln(λ) / shift
3.3201 0 0
0 2.2255 0
0 0 1.4918
λ =
0.12 0 0
0 0.08 0
0 0 0.04
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A consecutive reaction:
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No Expon. Decaying concn.
A B Dk1 k2
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Reaction model
First order, consecutive
CA,i = CA,0 e –k1 ti
CB,i = (e –k1 ti - e –k2 ti )k1 CB,0
k2- k1
CD,i = CA,0 - CA,i - CB,i
A B Dk1 k2
Columns of C matrix
cA
cB
cD
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X* = cA sAT + cB sB
T + cD sD
T + cL sL
T
= (e-k1t) sAT
+ k(e-k1t) sBT - k(e-k2t) sB
T
- (e-k1t)sD
T + e0tsD
T - k(e-k1t)sDT + k(e-k2t)sD
T
+ e0t sL
T
= e-k1t ( sA + k sB
- sD – k sD) T
+ e-k2t (- k sB + ksD)T
+ e0t (sD + sL )
T
Sum of exponentially decaying functions
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Unique decomp.
But not result into actual spectra and concn. profiles
= e-k1t ( sP + k sQ
- sR – k sR) T
+ e-k2t (- k sQ + ksR)T
+ e0t (sR + sL )
T
e1 e2 e3
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Trilinear structure
1
M-s
1+s
M
NX1
X2
= +
X
2-way
X
3-way
E
Gives k1 and k2
(MN)
((M-S) N 2)
Stacking
E
F
λ
Expon.Decaying
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X*
fA
eAT
fB
eBT
fD
eDT
= +
+ +
1..1
N+1
eLT =[0 0 .. 0 1]
fL =[e0 e0 .. e0]
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What if :
Not applying the
ones column?
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An Examplefor consecutive reaction
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0.99997 0 0
0 5.77 0
0 0 19.848
λ=
k = ln() / shift
0.0000 0 0
0 0.0701 0
0 0 0.1195
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Not proper pure spectra !
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Not proper pure conc. Prof.s !
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What about estimation of spectral and concentration profiles?
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An NMR example
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PGSE NMR
Pulsed Gradient Spin Echo NMR
A Mixture,
with exponential decay of the contribution of each component
A series of spectra
A function of diffusion coefficient of component
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Low-MW
Poly(dimethylsiloxane) PDMS
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MRI14 images
(echo times (TEs) from 15 to 210ms)
Exponential decay of signal from each component
=f(sp.-sp. relax. Time of compon.)
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Thanks