Understanding complex materials using high definition mass spectrometry

©2015 Waters Corporation 1

Understanding Complex Materials using High Definition Mass Spectrometry

Eleanor Riches, Ph.D. Principal Scientist

03 November 2014


Presentation Overview

Enhanced Structural Characterisation

Comparing Complex Samples

Overview of the SYNAPT G2-Si HDMS Instrument

Introduction to Ion Mobility & Collisional Cross Section

CCS: A Useful Identification Point


The SYNAPT G2-Si HDMS Instrument


SYNAPT G2-Si HDMS Technology: Ion sources


SYNAPT G2-Si HDMS Technology: Ion sources

MALDI

ESI

APCI

APPI

APGC

ASAP

DART

DESI

LDTD


SYNAPT G2-Si HDMS Technology: QuanToF

50k FWHM


SYNAPT G2-Si HDMS Technology: Ion mobility separation


Ion Mobility and Collisional Cross Section (CCS)


Turbomolecular Pumps

Trap IMS Transfer

Gate

N2

Ar

Ions In

Ions Out 0.05mbar

He

0.05mbar 3mbar

Travelling Wave ion mobility separation


C16H26 Branched structure

C16H26 Straight chain

structure

C7H8





structure

C7H8





structure

C7H8



Collision Cross Section (CCS) Ion mobility MS measures an ion’s DRIFT TIME

— Applying a calibration gives us COLLISION CROSS SECTION (CCS), a key physicochemical property of the species

Polyalanine calibration CCS value Measured

Drift Time


Collision Cross Section (CCS) Ion mobility MS measures an ion’s DRIFT TIME

— Applying a calibration gives us COLLISION CROSS SECTION (CCS), a key physicochemical property of the species

Time-of-Flight MS measures an ion’s FLIGHT TIME

— Applying a calibration gives us MASS TO CHARGE RATIO (m/z), and hence the ion’s mass: a key physicochemical property of the species

Polyalanine calibration CCS value Measured

Drift Time

Sodium formate calibration m/z value Measured

Flight Time


What is CCS?

• Chemical Structure

(mass, size)

• 3-dimensional Conformation

(shape)

Precise Physicochemical

Property of an ion

Important differentiating

Characteristic of an ion


CCS: A Useful Identification Point


CCS: a useful identification point

Matrix Rt (mins) %Error Pear 7.48 1.73

Boscalid expected retention time (Rt) 7.35 mins (standard): Matrix dependent retention time shifts



Matrix Rt (mins) %Error Pear 7.48 1.73 Mandarin 7.55 2.65




Matrix Rt (mins) %Error Pear 7.48 1.73 Mandarin 7.55 2.65 Leek 7.68 4.30




Matrix Rt (mins) %Error Pear 7.48 1.73 Mandarin 7.55 2.65 Leek 7.68 4.30 Ginger 7.78 5.53




Without CCS Without CCS With CCS m/z tolerance +/-

5ppm 10ppm 10ppm

Rt tolerance +/- 2.5% 2.5% 2.5% CCS tolerance +/-

- - 2%

Correct IDs 7 8 8 False negatives 1 0 0 False positives 1 1 0

Using CCS filtering: 0% false positives and false negatives observed for pesticide formulation

With thanks to Dr. Mike McCullagh


Enhanced Structural Characterisation


m/z

Drift time

Using the IMS region for fragmentation

Precursor ions separated

by IMS

m/z

Drift time

Precursor and product ions

are TIME ALIGNED


m/z

Drift time

m/z

Drift time

1st & 2nd generation product ions

are TIME ALIGNED

Ion isolated

by quadrupole

Product ions separated

by IMS

Precursor ion FRAGMENTED

Using the IMS region for fragmentation


BDAVBi Blue Dopant

C52H40N2

693

693

616

448 525

256 168

MS Spectrum

MS/MS Spectrum

356

N

N

Analysis of BDAVBi blue dopant



OLED01_045.raw : 1

168

356

256

448

616

525

693

Drift time (Bins)

m/z

Separation of isomers

N

N

Ion isolated

by quadrupole



OLED01_047.raw : 1

A

A B

B C

C D

D

Ion isolated

by quadrupole


MS/MS in petroleomics applications


MS/MS in petroleomics applications With thanks to Dr. Priscila Lalli, visiting researcher, NHMFL, FSU



[C13H22S + 107Ag]+, DBE = 3 Ion isolated

by quadrupole

-H2S

-H2S -C3H4

-CH2S

SHR

SR

With thanks to Dr. Priscila Lalli, visiting researcher, NHMFL, FSU



S1 Class, DBE = 3 With thanks to Dr. Priscila Lalli, visiting researcher, NHMFL, FSU


Comparing Complex Samples


Ion mobility data: Compared using HDMS Compare


Asphaltene Sample 1

Ion mobility data: Two different asphaltene samples

Asphaltene Sample 2






PMMA infusion, ESI-SYNAPT G2

With thanks to Kirsten Craven

Ion mobility data: Two different PMMA polymer samples


Polymerix

With thanks to Kirsten Craven


©2015 Waters Corporation 39 With thanks to Kirsten Craven



PetroOrg: Petroleum industry-specific software

With thanks to Dr. Yuri E. Corilo, Developer of PetroOrg software, FFI & Omics LLC


PetroOrg: Petroleum industry-specific software

Example of a Carbon Number vs DBE plot for the N1 Class

Example of a Van Krevelen diagram for the N1 Class

With thanks to Dr. Yuri E. Corilo, Developer of PetroOrg software, FFI & Omics LLC


Summary

Waters’ SYNAPT G2-Si HDMS instrument, with its quadrupole – ion mobility-ToF geometry, is an unrivalled tool for the characterisation of complex materials

The orthogonal separation offered by ion mobility enables powerful structural elucidation workflows

Collisional Cross Section (CCS) measurements provide valuable confirmatory data points

Ion mobility-specific software allows interactive data evaluation and processing

Partnering and collaborating with key thought leaders has resulted in the development of unique petroleum industry-specific data processing software


Thank you for your attention!

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Understanding complex materials using high definition mass spectrometry