getting rid of rayleigh
DESCRIPTION
Getting rid of Rayleigh. Åsmund Rinnan. Introduction Fluorescence. Emitted from sample. Excites sample. Sample. Light source. Detector. Introduction Fluorescence. Introduction PARAFAC. Can be seen as an expansion of PCA from two-way data to multi-way data. X is the EEM - PowerPoint PPT PresentationTRANSCRIPT
Getting rid of Rayleigh
Åsmund Rinnan
IntroductionFluorescence
Lightsource
Sample
Detector
Excitessample
Emittedfrom sample
IntroductionFluorescence
IntroductionPARAFAC
ijk
F
fkfjfifijk ecbax
1
X is the EEMa are the scoresb are the emissionspectrac are the excitationspectraE is the residuals
Can be seen as an expansion of PCA from two-way data to multi-way data
ij
F
fjfifij eptx
1
=
A
B
C
IntroductionPARAFAC & Fluorescence
IntroductionPARAFAC & Fluorescence
Catechol
Hydroquinone
Introduction”Faking” fluorescence
IntroductionLight scatter
IntroductionLight scatter – The trouble maker
Excita
tion
Emission
2n
d o
rder
Rayle
igh
1st
ord
er
Rayle
igh
Ram
an
IntroductionLight scatter
IntroductionBi-linearity
IntroductionWhy is this a problem?
X
X
ExampleFluorescence & PARAFAC
Getting rid of Rayleigh
•Subtraction of standard
•Cut off and insert missing/ zeros
•Weights•Modeling of Rayleigh
Subtracting a standard
Missing values
Missingvalues
Zeros
Signal/ Data area
Thygesen, Rinnan, Barsberg & Møller
Example
• 18 wood samples• 4 different levels of p-benzoquinone adsorbed in
the fiber cell walls• 30 emission wavelengths x 35 excitation
wavelengths
Thygesen, Rinnan, Barsberg & Møller
WOW!
None Weighted
Non-Negativity Zeros
So, now Rayleigh is finished, right?
• The data presented so far is a bit simple Sugar data
Excitation
Emission 1st o
rder
Ray
leig
h
Weighting - MILES
Emission loadings Excitation loadings
Band of missing values
Using a band of missing valuesHard weights
Emission loadings Excitation loadings
Using a band of missing valuesMILES weights
Emission loadings Excitation loadings
Another method?Why, why, why?
• The Rayleigh scatter width has to be estimated quite accurately
• The band width of missing data should also be correct
• What about an automatic method of removing the Rayleigh scatter, that was not so prone to the estimation of the width of the Rayleigh scatter?
• Modeling the Rayleigh is the answer!
Modeling Rayleigh
• A Gauss-Lorentz curve fitting method
Modeling Rayleigh
Rinnan, Booksh & Bro
Modeling Rayleigh
With constraints even better
Emission loadings Excitation loadings
Rinnan, Booksh & Bro
• Thanks to: Rasmus Bro, Karl Booksh, Lisbeth G Thygesen, Søren Barsberg, Jens K S Møller and Charlotte Andersen
• Thank you for your attention