Evolving Factor Analysis
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Transcript of Evolving Factor Analysis
Evolving Factor AnalysisThe evolution of a chemical system is gradually known by recording a new response vector at each stage of the process under study. EFA performs subsequent PCA on gradually increasing submatrices in the process direction, enlarged by adding one new row at a time. This procedure is performed from top to bottom of the data set (forward EFA) and from bottom to top (backward EFA) to investigate the emergence and the decay of the process contribution, respectively. The forward and backward EFA plots are built by representating the singular values of each PCA analysis vs. the process variable related to the last row included in the window analyzd.
1.4327 0.0024
Singular values (0-2 sec)
2.2664 0.0083 0.0000
Singular values (0-4 sec)
3.2730 0.0231 0.0000 0.0000
Singular values (0-6 sec)
4.4044 0.0563 0.0001 0.0000
Singular values (0-8 sec)
5.5834 0.1245 0.0004 0.0000
Singular values (0-10 sec)
6.7299 0.2517 0.0012 0.0000
Singular values (0-12 sec)
7.7864 0.4668 0.0036 0.0000
Singular values (0-14 sec)
8.7323 0.7956 0.0099 0.0000
Singular values (0-16 sec)
9.5808 1.2484 0.0244 0.0000
Singular values (0-18 sec)
10.3637 1.8119 0.0552 0.0000
Singular values (0-20 sec)
11.1136 2.4512 0.1133 0.0000
Singular values (0-22 sec)
11.8506 3.1232 0.2110 0.0000
Singular values (0-24 sec)
12.5772 3.7923 0.3561 0.0000
Singular values (0-26 sec)
13.2808 4.4360 0.5455 0.0000
Singular values (0-28 sec)
13.9413 5.0402 0.7623 0.0000
Singular values (0-30 sec)
14.5360 5.5893 0.9812 0.0000
Singular values (0-32 sec)
15.0430 6.0633 1.1776 0.0000
Singular values (0-34 sec)
15.4449 6.4435 1.3359 0.0000
Singular values (0- 36 sec)
15.7348 6.7216 1.4512 0.0000
Singular values (0- 38 sec)
15.9215 6.9040 1.5268 0.0000
Singular values (0- 40 sec)
16.0273 7.0098 1.5713 0.0000
Singular values (0- 42 sec)
16.0794 7.0634 1.5942 0.0000
Singular values (0- 44 sec)
16.1015 7.0868 1.6044 0.0000
Singular values (0- 46 sec)
16.1096 7.0955 1.6083 0.0000
Singular values (0-48 sec)
16.1122 7.0983 1.6096 0.0000
Singular values (0-50 sec)
0.7231 0.0017 0.000 0.000
Singular values (50-48 sec)
1.2648 0.0060 0.0000 0
Singular values (50-46 sec)
2.0245 0.0164 0.0000 0.0000
Singular values (50-44 sec)
3.0143 0.0395 0.0000 0.0000
Singular values (50-42 sec)
4.2074 0.0865 0.0001 0.0000
Singular values (50-40 sec)
5.5408 0.1738 0.0003 0.0000
Singular values (50-38 sec)
6.9305 0.3215 0.0009 0.0000
Singular values (50-36 sec)
8.2934 0.5483 0.0029 0.0000
Singular values (50-34 sec)
9.5650 0.8639 0.0082 0.0000
Singular values (50-32 sec)
10.7064 1.2627 0.0213 0.0000
Singular values (50-30 sec)
11.7008 1.7245 0.0504 0.0000
Singular values (50-28 sec)
12.5455 2.2228 0.1080 0.0000
Singular values (50-26 sec)
13.2478 2.7381 0.2091 0.0000
Singular values (50-24 sec)
13.8235 3.2656 0.3639 0.0000
Singular values (50-22 sec)
14.2956 3.8130 0.5684 0.0000
Singular values (50-20 sec)
14.6900 4.3880 0.8003 0.0000
Singular values (50-18 sec)
15.0288 4.9811 1.0266 0.0000
Singular values (50-16 sec)
15.3247 5.5579 1.2200 0.0000
Singular values (50-14 sec)
15.5782 6.0693 1.3680 0.0000
Singular values (50-12 sec)
15.7824 6.4753 1.4711 0.0000
Singular values (50-10 sec)
15.9307 6.7613 1.5372 0.0000
Singular values (50-8 sec)
16.0254 6.9387 1.5759 0.0000
Singular values (50-6 sec)
16.0776 7.0349 1.5963 0.0000
Singular values (50- 4 sec)
16.1022 7.0801 1.6058 0.0000
Singular values (50-2 sec)
16.1122 7.0983 1.6096 0.0000
Singular values (50-0 sec)
Using MATLAB for evolving factor analysis
hplc.m file
Creating HPLC-DAD data
HPLC-DAD data for three components system
EFA.m file
Evolving Factor Analysis
Ret
enti
on T
ime
Wavelength
D
Delete the SVF and SVB variables from the memory in work space
Creating the SVF matrix with (m m-1) dimensions and all elements equal to
zero
An example for zeros command in MATLAB
Plot the results of forward analysis
Change in order of columns of the matrix
Comparison of real and estimated profiles
?Employ the EFA in wavelength direction of data matrix and interpret the results
Transformation the concentration windows calculated with EFA to concentration profiles
Retention Time
C = S T
=
Con
cen
trat
ion
mat
rix
Scor
e m
atri
x
Transformation matrix
c1 = S t1
=
Con
cen
trat
ion
vec
tor
Scor
e m
atri
x
Transformation vector
=
c0 = S0 t1
0= t11 s1 + t21 s2 + t31 s3
HPLC-DAD data for three components system
Results from EFA
Retention Time
From row number 35 to 61
concEFA.m file for calculation the concentration
profiles according to results of EFA
Comparison the results with true values
?
Use the concEFA.m file and calculate the concentration profile for third component
Application of EFA in chemical equilibria study
Stepwise dissociation of triprotic acid H3A
H3A.m file
for simulating the spectrophotometric monitoring
of pH-meteric titration
Evolving Factor Analysis (EFA)
Evolving Factor Analysis (EFA)
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Use the H3A.m file and investigate the effects of pKas on results of EFA.
Application of EFA in chemical Linetics study
Consecutive reaction
consecutive.m file
for simulating the spectrophotometric monitoring of consecutive A B C reaction
Evolving Factor Analysis (EFA)
Evolving Factor Analysis (EFA)
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Use the consecutive.m file and investigate the effects of rate constants on results of EFA.
Fixed concentration of interference and EFA
EFA
HPLC-DAD data after column mean centering
Results of forward and backward eigen analysis
Results of applying EFA on mean centered data
Score plot without mean centering
Score plot after mean centering
Distribution of objects of a two component system
O A2
A1
Mean centering
O A1
A2
Mean centering and then PCA
O
PC1PC2
Distribution of objects of a two component system
O A1
A2
Mean centering on window data
O A1
A2
Before appearance the analyte the variance is equal to zero
Mean centering on window data and then PCA
O PC1
PC2
Before appearance the analyte the variance is equal to zero
Mean centering on window data and then PCA
O PC1
PC2
O PC1
PC2
Before appearance the analyte the variance is equal to zero
Mean centering on window data and then PCA
Before appearance the analyte the variance is equal to zero
Mean centering on window data and then PCA
O PC1
PC2
Mean centering on window data
O A1
A2
Mean centering and then PCA on window data
O
PC1PC2
Mean centering on window data
O A1
A2
Mean centering and then PCA on window data
O
PC1PC2
Mean centering on window data
O A1
A2
Mean centering and then PCA on window data
O
PC1PC2
IEFA.m
Evolving factor analysis in the presence of fixed concentration
interferent
Results of applying IEFA.m file
Results of applying IEFA.m file
Comparison between results of IEFA and real values of analyte
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Use IEFA.m file and analyze the three co-eluting components system with fix concentration of one of them
Titration of H3A in the presence of an inert species
Titration of H3A in the presence of an inert species
EFA results
EFA results in the absence of interference
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WHY?