Compositional Analysis of Whole Soybean Grain by Transmission Raman Spectroscopy: A Pilot Study

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Compositional Analysis of Whole Soybean Grain by
Transmission Raman Spectroscopy A Pilot Study
-- Matthew Schulmerich --
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Business Vision
Define

• The U.S. Soybean industry is a 28 billion/year
  business, however emerging markets (Brazil and
  Argentina) are creating significant pressures
  that are shifting the world percentage of soybean
  production.
• Because soybeans are more widely available the US
  market is looking for ways to add value to their
  products that can offset the industries maturing
  market.
• One way to do this is through quality control of
  grain. Well characterized grain can be sold at
  premium prices.
• While this work is a pilot study and not a
  business proposal, there is interest in the
  development of soybean quality control
  instrumentation by both the national soybean
  board and the FDA. Instrumentation developed for
  soybean quality control can also be extended to
  other crops.

Define business vision
Define problem statement
Define External CTQ's
Scope
Develop core project team
Stakeholder analysis
Develop High Level Communication Plan
Project Timeline and project plan
3
Problem Statement
Define

• Reliable measure of economically important
  soybean grain components is an important concern
  in the soybean industry. The current technology
  standard (NIR spectroscopy) does not provide the
  precision desired by the industry. Precision is
  important because
• In commercial trade, uncertainty in analysis of
  grain components can cause major losses in grain
  elevators in recouping premiums paid for a
  particular seed component.
• Discrepancies between grain buyers and sellers
  can bring export shipments to a halt or require
  major concessions by one or both parties,
  potentially blemishing future opportunities.
• Commodity merchandisers and grain processors
  depend on valid analyses of product value.
• Soybean breeders attempting to develop and
  improve grain quality require reliable
  information about grain composition.
• Laboratories providing grain industry services
  and maintaining laboratory accreditation rely on
  the latest, industry-approved technologies to
  ensure quality, precision, and accuracy.

Define business vision
Define problem statement
Define External CTQ's
Scope
Develop core project team
Stakeholder analysis
Develop High Level Communication Plan
Project Timeline and project plan
4
How do you characterize Soybeans?
NIR Spectra
Detector
Soybean
Current Technology uses Near Infrared Spectroscopy
J. Agric. Food Chem., Vol. 54, No 19, 2006
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Our thoughts Maybe NIR is not the best choice
Radio
Medium
Cosmic
Gamma
X
UV
IR
Micro
UHF
Short
Long
Ultra violet
Infrared
Vis
Mid
Far
Near
400
750
2,500
16,000
1,000,000
nm
1
-Near Infrared Spectroscopy- 750-2,000nm-Mid
Infrared Spectrocopy- 2,000nm-25,000nm
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Vibrational Spectroscopy (IR gives more specific
chemical information)
IR Spectra
Detector
Soybean
11,000nm
2,500nm
Lipid Technology Vol. 19, No. 4, 2007
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Soybean Study (Preliminary data)
For each of the four seed types 2 sections were
taken

• Sectioning for IR and Raman Measurements
• Sample preparation Soybeans were sectioned to be
  5 micron sections and put on a CaF2 disk.
• Two sections were acquired from each of the four
  seed types (below). Both cotyledons were visible
  in each section

(1mm2)
8 point Raman measurements were acquired for
each section using 785nm laser
I am working on getting a better image of this,
but the microscope I need to use is currently not
working
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Four soybean varietiesIR images and NIR data
IR Images- Amide I/CH2 (represents Protein/Lipid)
The four bean types have very different chemical
distributions (n2 for each type)
Protein data is average of 14 field locations 2
reps per location NIR technology LSD
(0.05)0.50.
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Vibrational Spectroscopy (Raman is a different
type of spectroscopy)
Detector
785nm
Soybean
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Raman Spectroscopy
786nm
Molecules in the soybean
787nm
788nm
789nm
790nm
791nm
792nm
793nm
794nm
795nm
796nm
797nm
798nm
799nm
800nm
801nm
802nm
Detector
803nm
804nm
805nm
806nm


785nm
Soybean
Detector Array
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Raman Spectroscopy
786nm
Molecule in the soybean
787nm
788nm
785nm light is rejected
789nm
790nm
791nm
792nm
793nm
794nm
795nm
796nm
797nm
798nm
799nm
800nm
801nm
802nm
Detector
803nm
804nm
805nm
806nm


785nm
Soybean
Detector Array
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Raman Spectroscopy
786nm
Molecules in the soybean
787nm
788nm
789nm
790nm
791nm
792nm
793nm
794nm
795nm
796nm
797nm
798nm
799nm
800nm
801nm
802nm
Detector
803nm
804nm
805nm
806nm


785nm
Soybean
Detector Array
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Raman Spectroscopy
786nm
gt785nm light passes through And get directed to a
detector channel
Molecule in the soybean
787nm
788nm
789nm
790nm
791nm
792nm
793nm
794nm
795nm
796nm
797nm
798nm
799nm
800nm
801nm
802nm
Detector
803nm
804nm
805nm
806nm


785nm
Soybean
Detector Array
14
Raman Spectroscopy
786nm
lt785nm light passes through And get directed to a
detector channel
Molecule in the soybean
787nm
788nm
789nm
790nm
791nm
792nm
793nm
794nm
795nm
796nm
797nm
798nm
799nm
800nm
801nm
802nm
Detector
803nm
804nm
805nm
806nm


785nm
Soybean
Detector Array
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Raman Spectroscopy
786nm
787nm
788nm
789nm
Billions of 785nm photons
790nm
Molecules in the soybean
791nm
792nm
793nm
794nm
795nm
796nm
797nm
798nm
799nm
800nm
801nm
802nm
Detector
803nm
804nm
805nm
806nm


785nm
Soybean
Detector Array
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Soybean Raman Spectrum
Raman Intensity (A.U.)
Raman Shift (cm-1)
810nm
915nm
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NIR Vs- IR Vs- Raman Spectroscopy

• NIR Light tends to scatter more than it is
  absorbed so you have greater penetration depth
• The spectral information arises from broad
  spectral overtones and as a result it is
  difficult to assign spectral features to specific
  chemical components
• Light scattering tends to be a problem
  corrections are needed

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NIR Vs- IR Vs- Raman Spectroscopy

• IR Light tends to absorb more than it scatters
  so you have very little penetration depth
• The spectral information arises from narrower
  spectral overtones and as a result you can assign
  spectral features to specific chemical components
• Sample thickness tends to be the biggest
  difficulty with IR spectroscopy

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NIR Vs- IR Vs- Raman Spectroscopy

• Raman can use any single wavelength of light
• Raman has narrow band and as a result achieves
  very high chemical sensitivity (band can be
  assigned to specific molecular groups)
• Quantum efficiency is low for Raman spectroscopy
  (longer acquisition times)

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Information that is obtainable Linear
combinations
785nm
Polyethylene
15 mm
Delrin
Teflon
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Information that is obtainable
Beers Law
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Soybean Study (Preliminary data)
Raman Point Measurements
RCHCHR
Phenylalanine
CH2 Stretch
RCONH2
Raman Intensity (A.U.)
C-C
RCOOR
C-C
Raman Shift (cm-1)
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Soybean Study (Preliminary Data)
Transmission Measurements
Phenylalanine
CH2 Stretch
Soybean
Funded
Raman Intensity (A.U.)
785nm Laser
offset for comparison
Collection Optics
Raman Shift (cm-1)
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Critical to Quality (Whats important?)

Define
Define problem statement
Pre-engineering
Define business vision
- Whole grain sample analysis ? the goal is bulk
samples (100 soybeans)
Define External CTQ's

• Fast analysis time (1-5 minutes) ? Hyper
  spectral data acquisition

- Precise composition information ? calibration
curve developed w/ single grain
Scope
Post-engineering
Develop core project team
- Robust instrumentation ? engineering and
packaging
- User friendly ? software
Stakeholder analysis
- Repeatable and Reproducible data ? software,
packaging, and training
Develop High Level Communication Plan
Project Timeline and project plan
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The scope of this study

Define

• To determine if Raman spectroscopy can predict
  compositional analysis of multiple attributes
  contained in whole soybean grain samples with
  greater precision and/or accuracy than can
  conventional near infrared reflectance (NIR)
  spectroscopy.
• The specific research objectives are
• Build the instrumentation necessary to achieve
  transmission measurements on whole soybean grain.
• Develop a calibration model for soybean protein
  and oil.
• Study the impact of ambient water in
  transmission Raman spectroscopy of soybeans.
• Deliverables A robust, repeatable, reproducible
  calibration model and associated instrumentation
  to quantify the protein and oil components of
  whole soybean grain.

Define problem statement
Define business vision
Define External CTQ's
Scope
Develop core project team
Stakeholder analysis
Develop High Level Communication Plan
Project Timeline and project plan
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Project Team and Stakeholders

Define

• Core Project Team
• Raman Instrumentation, measurements, and modeling
• Matt Schulmerich, Rohit Bhargava
• NIR Measurements and Calibration data
• John McKinney, Dennis Thompson
• National Soybean Research Center
• Linda Kull, Peter Goldsmith
• Stakeholders
• University of Illinois at Urbana Champaign
• United Soybean Board

Define problem statement
Define business vision
Define External CTQ's
Scope
Develop core project team
Stakeholder analysis
Develop High Level Communication Plan
Project Timeline and project plan
27
Communication Plan
Define
Define problem statement
You?
Define business vision
Define External CTQ's
Define
Discuss objectives, budget, purchasing, and
timeline
Meeting 1
Scope
Discuss Instrumentation performance And
measurement timeline
Develop core project team
Design
Build
Measure
Meeting 2
Stakeholder analysis
Discuss model parameters and verification approach
Calib. Meas.
Model
Analyze
Meeting 3
Develop High Level Communication Plan
Verify
Reproducibility
Repeatability
Discuss results and next steps
Project Timeline and project plan
Meeting 4
Document results, patents and publication
Control
Meeting 5
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Project Timeline and Project Plan
Define
Define problem statement
Define
November 2009
Meeting 1
Define business vision
Define External CTQ's
Design
Build
Measure
January 2010
Meeting 2
Scope
May 2010
Develop core project team
Calib. Meas.
Model
Analyze
Meeting 3
Stakeholder analysis
Verify
Reproducibility
Repeatability
June 2010
Meeting 4
Develop High Level Communication Plan
Control
Project Timeline and project plan
August 2010
Meeting 5
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Your Part
Define
Design
Build
Measure
January 2010
Meeting 2
Define problem statement
Define business vision
Define External CTQ's
-Experimental Design -Optical Modeling
(Zemax) -Instrumental design and
Construction -Measurements -Calibration Model
Scope
Develop core project team
Stakeholder analysis
Develop High Level Communication Plan
My contact info
Matthew Schulmerich schulmer_at_illinois.edu
Project Timeline and project plan