Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates...
Transcript of Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates...
![Page 1: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/1.jpg)
GC-APCI/IMS-QTOF for the Analysis of Diesel
Sheher Bano MohsinDavid WongRob Ley
![Page 2: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/2.jpg)
Why EPA Regulates Diesel Fuel
The amount of sulfur in diesel fuel is directly linked to the amount of pollution produced when the fuel is burned in an engine. Higher levels of sulfur increase pollutants.
![Page 3: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/3.jpg)
Practical Advances in Petroleum
Processing, Volume 1
edited by Chang Samuel Hsu, Paul Robinson
![Page 4: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/4.jpg)
• Instrumentation – IM-QTOF with GC1. Instrument Overview
2. Benefits of IM
• Results
Things to Cover
![Page 5: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/5.jpg)
•Increases MS flexibility by enabling both GC and LC MS
•Analysis of wider range of compounds
•Proven QTOF LC/MS platform
•Proven 7890 GC performance
G3212A- GC APCI Interface
Page 5
0
![Page 6: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/6.jpg)
IM-QTOF Instrument Overview
6
• System sensitivity optimized using electrodynamic ion funnels to focus and transmit ions
• Ion Mobility resolution optimized while maintaining QTOF performance (mass resolution and accuracy)
• Ion Fragmentation can be selected using standard QTOF collision cell (CID)
• Bandwidth of QTOF data acquisition and processing channel was increased by 10 fold to match the ion mobility data rates
![Page 7: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/7.jpg)
Ion Mobility System Design
7
Ionization source: Ion generation (ESI, AJS, Nano ESI, ChipCube, GC-APCI etc.)
Front ion funnel: Efficient ion collection, desolvation and excess gas removal
Trap funnel: Ion accumulation and introducing ion packets into drift cell
Drift cell: Uniform low field ion mobility allows direct determination of accurate CCS (Ω)
Rear funnel: Efficient ion refocusing and introduction into mass analyzer
![Page 8: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/8.jpg)
Benefits of Adding Ion Mobility to GC/Q-TOF/MS
• Adds Additional Separation Power • A new dimension of separation for increased mass spectral
purity especially for complex mixture analysis
• Improves Detection Limits • Helps to eliminate interference from other analytes and
background in the sample mixture
• Efficient ion focusing and transfer through the ion optics maximizes sensitivity for the overall system
• Enhances Compound Identification
• Improves confidence in compound identification and ion
structure correlation through accurate collision cross section
measurements
8
![Page 9: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/9.jpg)
Excellent in Resolution and Separation Power
9
Chromatography Ion Mobility Mass
~ minutes ~ 60 milli-seconds ~ 100 m seconds
![Page 10: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/10.jpg)
IMS fits between LC and TOF MS on the separation time scale
Adding Ion Mobility Spectrometry
An Additional Dimension of Full Spectral Specificity
Mass Spectrum
Signal Response
Agilent Restricted Page 10
Chromatogram ~ minutes
Drift Spectrum ~ 60 msec
Mass Spectra ~ 100-200 usec
![Page 11: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/11.jpg)
tdrift
Detector
AnalyteIons
GatingOptics
Ion Mobility Cell
t0
VH VL
Electric Field
Stacked ring ion guide gives linear field
Basic Operational Principle of Ion MobilityFor Conventional DC Uniform Field IMS
June 27, 2016 11
𝑣 = 𝐾 𝐸 ∝𝑒 𝐸
𝑃 𝑇 Ω
![Page 12: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/12.jpg)
Resolving Structural Sugar Isomers C18H32O16
June 27, 2016 12
Melezitose
Raffinose
Resolving two isobaric trisaccharides
![Page 13: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/13.jpg)
Conformational Space Occupancy of Biomolecules
Co
llis
ion
Cro
ss S
ecti
on
(Å2)
Mass (Da)
Hypothetical Ordering ofBiomolecular Classes
lipids
carbohydrates
peptides
oligonucleotides
![Page 14: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/14.jpg)
Lipid Analysis
Tetraalkylammonium Salts+2 ions
+3 ions
+1 ions
+4 ions
Ion
Mo
bilit
y D
rift
Tim
e (
ms)
Mass (Da)
0
0
20
40
50
500 1000 1500 2000
10
30
60
70
L-α-phosphotidylethanolamines (PE)
TAA-3
TAA-16
TAA-12
TAA-10
TAA-8TAA-7
TAA-6TAA-5
TAA-4
![Page 15: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/15.jpg)
GC-APCI-IMS of Diesel
![Page 16: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/16.jpg)
C12H8S
C14H12SC13H10S
C15H14S
C16H14S
![Page 17: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/17.jpg)
Extracting the dibenzothiophenes(Mass defect below 0.1 amu)
Diesel B
Diesel C
![Page 18: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/18.jpg)
Kendrick Mass Defect Plot showing series of related compounds with
same Kendrick mass Defect
184 198 212 226 240 254
![Page 19: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/19.jpg)
Dibenzothiophenes in Diesel Sample before HDS
![Page 20: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/20.jpg)
Comparing Diesel B to C
![Page 21: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/21.jpg)
Comparing elution profile in the same retention time window for the treated and untreated samples
![Page 22: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/22.jpg)
Chromatogram of Diesel sample before HDS
![Page 23: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/23.jpg)
Focusing on one area of the map
![Page 24: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/24.jpg)
Kendrick Plot showing Background and 4,6-DBT with their respective different mass defects
![Page 25: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/25.jpg)
Species separated out by different drift times
![Page 26: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/26.jpg)
Sulfur and Desulfurized Compounds
![Page 27: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/27.jpg)
C13H10S
![Page 28: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/28.jpg)
Ring Structures with Sulfur
![Page 29: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/29.jpg)
Drift Spectra
![Page 30: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/30.jpg)
Drift Spectra of a series
![Page 31: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/31.jpg)
C9H8S
![Page 32: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/32.jpg)
Complexity around 149 m/z
![Page 33: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/33.jpg)
Deisel Sample after HDS
![Page 34: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/34.jpg)
Focusing on a small area
![Page 35: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/35.jpg)
Kendrick Mass Defect for a series of related Compounds with KMD of 0.1008
![Page 36: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/36.jpg)
C12H8, C13H10, C14H12, C15H14, C16H16, C17H18 etc
C15H18
C15H16
C15H20C15H22
![Page 37: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/37.jpg)
IMS map for molecular weights from m/z 178 - m/z 232
![Page 38: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/38.jpg)
Addition of methyl group within a C15 series
C15H18C15H20
C15H22
C15H16
C15H14
C15H12
![Page 39: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/39.jpg)
Extracting a thin slice of the chromatogram
Several Possible Structures
4.4 minutes
![Page 40: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/40.jpg)
3.4 minutes
![Page 41: Sheher Bano Mohsin David Wong Rob Ley...Sheher Bano Mohsin David Wong Rob Ley Why EPA Regulates Diesel Fuel The amount of sulfur in diesel fuel is directly linked to the amount of](https://reader033.fdocuments.us/reader033/viewer/2022042418/5f34a37efe60cc3abe01b38e/html5/thumbnails/41.jpg)
• IM-QTOF with the GC-APCI interface can be used to study HDS
Conclusions• IM-QTOF with the GC-APCI interface can be used to study HDS
Acknowledgements
• Ken Imatani
• David Wong
• Rob Ley