Near-Infrared Spectroscopy: Analytical Applications, Research and … · Practical Guide and...
Transcript of Near-Infrared Spectroscopy: Analytical Applications, Research and … · Practical Guide and...
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H. W. Siesler Department of Physical Chemistry University of Duisburg-Essen D 45117 Essen, Germany
Near-Infrared Spectroscopy: Analytical Applications, Research and
Process Control
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Outline of the Presentation
Introduction
Some qualitative aspects of NIR spectroscopy
Miniaturization
Conclusions
Selected research and quality/process control applications by NIR spectroscopy
Introduction
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Today NIR Spectroscpy is Ubiquitous
Agriculture Food Chemistry Polymers Petrochemistry Pharmaceuticals Medicine Environment Geology
This is also reflected in the number of globally sold units (2011):near-IR: ~ 8500 (~ $ Mil 225)mid-IR: ~ 10000 (~ $ Mil 450)
Notwithstanding these facts there is still a lot of persuading to do.
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The Principles of MIR NIR
m1 m2
NEAR-INFRARED
OVERTONES/COMBINATIONS12500 – 4000 cm-1
0.8 – 2.5 m
V
q
ANHARMONICITYm2 << m1
0
q /
FUNCTIONALITIESCH / OH / NH
MID-INFRARED
FUNDAMENTALS4000 – 400 cm-1
2.5 – 25 m
V
qn = 0n = 1n = 2
n = 3
0q
ALL POLARFUNCTIONALITIES
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100
50
Tran
smitt
ance
(%)
Wavenumber (cm-1)40000
3000 2000 1500 1000 500
(C-F)
2 x (C-F)(CH2)
The Most Striking Case: MIR NIR-(CF2-CF2)n - (Teflon ™)
log
1/R
Wavenumber (cm-1)12000 8000 400010000 6000
00.
20.
4
(CH2) + (CH2)
Nonabsorbing referencefor NIR spectroscopy !!!
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Outline of the Presentation
Some qualitative aspects of NIR spectroscopy
Miniaturization
Conclusions
Selected research and quality/process control applications by NIR spectroscopy
Introduction
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Interpretation of MIR/NIR Spectra(CH3CH2COCH3 + 5% H2O)
J. Workman Jr., L. WeyerPractical Guide and Spectral Atlas
for Interpretive Near-Infrared Spectroscopy (2nd ed.)CRC Press, Boca Raton (2012)
MIR
1.0
0.8
0.6
0.4
0.2
0.0
NIR
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“NIR spectra have only broad absorption bands“
0.0
1.0
2.0A
bsor
banc
e
Wavenumber (cm-1)
Wavenumber (cm-1)
0.0
0.2
0.4
0.6
Abs
orba
nce
O Si
CH3
CH3n
Poly(dimethylsiloxane)
(Si-O)
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a
b
a-b
PDMS/PU70/30 %(w/w)
PDMS/PU57/43 %(w/w)
Interpretive Aspects of NIR Spectra
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Interpretive Aspects of MIR/NIR Spectra
Wavenumber (cm-1)10000 8000 6000 4000
Abs
orba
nce
2.0
1.0
0.0
NIRCH2-specific
CH3-specific
MIRButylglycolacetate
Butyldiglycolacetate
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(CH3) (CH2) (CH2)
(CH3)
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Outline of the Presentation
Some qualitative aspects of NIR spectroscopy
Miniaturization
Conclusions
Selected research and quality/process control applications by NIR spectroscopy
Introduction
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Driving Forces for the Implementation of NIR
The acceptance of NIR-spectroscopy for research and quality/process control has steadily increased because of:
••• time savings in comparison to other analyticaltechniques
••• simplified or no sample handling of toxic samples
••• measurement flexibility in hostile environments
••• speed of data acquisition
The following exemplary applications will demonstrate theversatility of NIR spectroscopy for these applications.
••• occasionally higher selectivity than MIR
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Organic OH-Functionality H2OContrary to MIR spectroscopy in the NIR spectra the bands of organic OH-groups are separated from the water bands.
This is of importance for polymer quality control applications:Simultaneous determination of OH-number and water content.
How can you discriminate: Upon peracetylation the band of the organic OH-group disappears.
NIR spectra of a polyetherwith different OH-number
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OH/NH-Functionalities
Contrary to MIR spectroscopy in the NIR spectra the bands of organic OH- and NH-groups are separated.
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Polymorphism Pharmaceutical Industry
• Polymorphism is the ability of a substance to exist in two or more crystalline forms.
• More than half of the drug substances described in monographs crystallize in more than one solid form.
• Solid state properties of active ingredients have a direct impact on: bioavailability/quality/efficacy safety/patent situation
• What analytical techniques are available for the rapid discrimination of different polymorphs ?
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__________________________________A Case Study of Polymorphism in a Pharmaceutical Active
(cooperation with A. P. Ayala, Fortaleza, Brazil)
Mebendazole
• Broad-spectrum anthelmintic against worms
• Three polymorphs (A, B, C): solubility B > C > A
• Therapeutic trials: A is inactive Publications: B is toxic
• USP test is not able to distinguish between forms A and C.
• polymorph C is pharmaceuticallypreferred
WHO estimates that one quarter of the world’s population is infected with one or more of the parasites.
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Detection of Polymorphism in Mebendazole: X-Ray Diffraction, Raman, NIR and MIR Spectroscopy
Form C
Form B
Form A
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X-Ray
Inte
nsity
2
Form A
Form B
Form CFT-NIR
log
1/R
Form A
Form B
Form C
FT-IR
500 1500
FT-RamanForm C
Form B
Form A
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Analysis of Phosgene in o-Dichlorobenzene Solutions
Because it is a highly toxic gas, it had to be analyzed off-line under extreme precaution measures (gas mask etc.)
NIR in-line control has alleviated the situation significantly.
Phosgene (COCl2) is used extensivelyin the production of isocyanates:
Synthesis: CO + Cl2 COCl2
COCl2
3 x ν(C=O)
- 2 HClR-NH2 + COCl2 R-N=C=O
Toxic Reaction: COCl2 + H2O 2 HCl + CO2
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NIR-Spectroscopic On/In-Line Determination of HF and HNO3in Si Wafer Etching Solutions of the Semiconductor Industry
Teflon is transparent in the NIR.
ABB BomemFT-NIR spectrometer
Teflon Tubing
Fiber Optic Cables
ClippirTransmission Cell
The etching solution is circulated in an all-Teflon™ closed loop.
tube diameter can be squeezedto the suitable thickness
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The Spectral Calibration Range Aquaphotomics !!!
Wavenumbers (cm-1)
Abs
orba
nce
3 x ν(OH) 2 x ν(OH) + δ(OH)
HNO3 69%(w/w)
HF 48 % (w/w)
H2O
industrial etching solution
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Polymer Recycling by NIR Spectroscopy
NIR-Spectrometer
NIR-Source
Conveyor Belt
( 3 m/s)
Monitoring Lamps
Separation Control
Air Jets
Unidentified Objects
Separation Modules
PE
PE
PP PVC PS PET
PETPSPVCPP
Approximately 95% of the polymer waste is correctly identified.
No other technique could cope with this task.
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256 Diode Array Wavelength Range: 1100 – 2100 nm Integration time: typical: 3 -10 ms Background: Spectralon
VisioNIR
In a Continuous Mixer (Blend Uniformity) On the Tablet Press (Content Uniformity)
On-Line Control of Pharmaceutical Processes by NIR Spectroscopy
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Technical Information: Continuous Mixer Continuous Mixer: KM5
Lödige GmbH, Paderborn, Germany Flow Rate: 10 - 300 kg/h Dwell Time: 10-30 s
Side View Front View
light fiber optics behindsapphire window
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Technical Information: Tablet Press
Tablet Press: Fette 102i Fette Compacting, Schwarzenbek, Germany
Tableting Velocity: 18.000 – 216.000 Tab/h (-120 Rot./min)Standard: 150.000 Tab/h (80 Rot./min)
Time between Tablets: app. 18 - 50 ms (20 - 55 Hz)
Total View
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The VisioNIR Fiber Probe for the Tablet Press
Collection Fiber
Illumination Fiber
Air Tubes
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Implementation of the VisioNIR Probe into the Tablet Press
Illumination Fiber
Air Tubes
Collection Fiber
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The Overall Test Set-Up
Dosing Head (Schenk)
Continuous Mixer (Lödige)
VisioNIR for Mixer (VisioTec)
VisioNIR for Tablet Press (VisioTec)
Tablet Press (Fette)
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Method Development for the Mixer
API content in the specified range (e.g. 20 - 30%, target content was 25%)
On-line monitoring of the mixed powders with the typical process variations
NIR spectra acquisition of the mixed product in 1% intervals (20 - 30%)
Sampling for Reference Analysis (UV)
74% Lactose
25% Paracetamol
1% MgSt
Investigated Formulation
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NIR Spectra of the Powder from Mixer
1100 2100 Wavelength (nm)
Data Pretreatment: SNVIn
tens
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Intensity
Diodes
Paracetamol
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PLS Model for Active Ingredient (Mixer)Regression Coefficient
1100 nm Wavelength 2100 nmPredicted vs. Reference Plot
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Method Development for the Tablet Press
On-line monitoring of the compressed tablets with the typical processvariations and variation of the compression force and the tableting speed
API content in the specified range between 20 - 30% (target content 25%)
NIR spectra acquisition of tablets with API contents 20 - 30% (1% intervals)
Sampling for Reference Analysis (UV)
74% Lactose
25% Paracetamol
1% MgSt
Investigated Formulation
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PLS Model for Active Ingredient (Tablet Press)
Predicted vs. Reference Plot
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Prediction of the API During the Test Run
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0:00 0:10 0:20 0:30 0:40 0:50 1:00 1:10 1:20 1:30
API con
tent [%
]
Time [h:min]
Phase 1 Phase 2 Phase 3 Phase 4 Phase 5 Phase 6 Phase 7 Phase 8 Phase 9 Phase10 Ph.11 Ph.12
0:00 0:10 0:20 0:30 0:40 0:50 1:00 1:10 1:20 1:30
Time (h:min)1:40
API
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tent
(% w
/w)
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Continuous Mixer / Tablet Press RMSEP > 1%
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Outline of the Presentation
Introduction
Some qualitative aspects of NIR spectroscopy
Miniaturization
Conclusions
Selected research and quality/process control applications by NIR spectroscopy
Introduction
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__________________________________Miniaturization of IR/NIR-Spectrometers 1975 2015
~ 250 kg
Nicolet FT-IR 1975
VIAVI Solutions (formerly JDSU)
2015
On-Site Analysis
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i-Spec Nano by B&W Tek
Preliminary Specifications
calibrationvalidation
PLS calibration for % fat in soybeans spectral range: 1350 - 1700 nm
Further New Development
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https://www.consumerphysics.com/myscio/
A Word of Caution
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http://tellspec.com/
Beam your health up !
A Word of Caution
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A Word of Caution
http://biozoom.net/de/A Health Data Revolution
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Conclusions
NIR spectroscopy has become a mature and extremely versatile technique that can be applied to solve a multiplicity of researchand quality/process control problems.
Despite this positive development a further improvement of theacceptance and recognition of this technique can be achieved by:
■ intensified communication between spectroscopists, agro- and food-oriented users and chemometricians
■ better understanding of the basic issues (band assignments, spectra pretreatments, use of alternative techniques, etc.).
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Acknowledgements
Frank Pfeifer, Laima Thimm, Sylvia Iwascek, Sedakat Altinpinar Damir Sorak, Uwe Hoffmann, Lars Herberholz, Olga KolomietsUniversity of Duisburg-Essen, Essen, Germany
ABB-Bomem, Quebec, CanadaBruker Optik GmbH, Ettlingen, GermanyBüchi GmbH, Essen, GermanyUhlmann VisioTec, Laupheim, GermanyVIAVI Solutions (formerly JDSU), Santa Rosa, USA
W. Hoehe, Uhlmann VisioTec GmbH, Laupheim, Germany
Kristiina Järvinen, Maiju Järvinen, School of Pharmacy, Faculty of HealthSciences University of Eastern Finland, Kuopio, Finland
M. Tondar, Glatt GmbH, Binzen, Germany
Fette Compacting, Schwarzenbek, Germany
Gebrueder Loedige Maschinenbau GmbH, Paderborn, Germany