an expanding gas phase portfolio - agilent an expanding gas phase portfolio for your expanding...

1

An Expanding Gas

Phase Portfolio For your expanding Analytical

Needs

January 8, 2013

Agilent Confidential

Badr Astiphan

GCMS Product Sales Specialist

1-866-524-7936

302-290-5631 cell

[email protected]

Agilent Restricted

Page 3

5975C SQ 7890 GC

2007

Agilent GC/MS Portfolio

January 8, 2013


4

5975E SQ 7820 GC

5975T LTM SQ

7000 TQ 7890 GC

240 IT 7890 GC

5977A SQ 7890B GC

7200 Q-TOF 7890GC

More Choices – Better Solutions

Agilent GC/MS/MS

Agilent GC/MS

January 8, 2013


5

Perf

orm

an

ce

240 IT 7890 GC

7000 TQ 7890 GC

5977A SQ 7890 GC

220 IT 7890 GC

5975E SQ 7820 GC

with Tray support

Q-TOF 7890 GC

5975T SQ

LTM GC

Price


January 8, 2013


6

MassHunter GC/MS Acquisition for GC/MSD

Unified GC/MS Acquisition and

MassHunter Data Analysis; with

MSD ChemStation workflow for GC/MSD

Agilent 5977 MSD

January 8, 2013


7

Proven Technologies Improving the Industry Standards for GC/SQ

Gold Quartz Quad Triple Axis Detector

High Temperature

Inert Source

Unique Entrance

Lens Design

All of 5975’s features also built in 5977, such as “Gold Quad”, SIM/Scan, Gain

tuning, Triple-Axis Detector, Trace Ion Detection, Auto CI, etc..

January 8, 2013


8

January 8, 2013


9

GC/MSD Software MassHunter Qual

MassHunter Quant MH

CS

MassHunter GC/MS Acquisition

And Use Either

MassHunter Data Analysis

OR

MSD ChemStation Data Analysis MSD ChemStation DA

G1701FA


Page 10

Market’s Best S/N (SNR) > 1500:1

Market’s Best Scan Rate = 20,000 u/s

Market’s ONLY IDL < 10 fg

Better from Agilent

Statistical confirmation of entire system’s

performance

January 8, 2013

Agilent Restricted

Page 11

7000B Triple Quad GC/MS

Ultimate tool for the

analysis of trace level

components in complex

matrix

Dedicated GC MS/MS system

Why a Quadrupole GC/MS/MS System?

• Lower detection limits in complex matrices than SQ scan

or SIM

• Accurate quantitation of target compounds even in high

chemical background samples

• Better precision and linearity than ion trap MS/MS

GC/MS Triple Quad (QQQ) for GC/MS/MS

Detector Quad 1

Mass Analysis

Collision Gas (Ar, N2, He)

Quad 2

Collision Cell

Ion Source

•Ionize Quad 3

Mass Analysis

Carrier Gas (He, H2 )

Mean Free

Path Long Long Short

Collisions No No Yes

MS MS

MS/MS Succeeds Where MS Fails

GC/MS Triple Quad SRM

GC/MS Single Quad SIM

A chromatographer’s

dream: single peak on

flat baseline

Interfering matrix

peaks = chemical

noise

7000 Series Quadrupole MS/MS

Optimized for Gas Chromatography How to Set Up an MS/MS experiment

EI Spectrum with

all analyte and

background ions

How to Set Up an MS/MS experiment


Optimized for Gas Chromatography

Q1 mass filters all

ions other than the

precursor; only

target ion 210

pass through



Collision cell

dissociates m/z 210

into product ions



Q2 monitors only

characteristic fragments

158 and 191 from m/z

210 for quant and qual

MS/MS Eliminates Scan and SIM Interferences

analyte

Product 1 Product 3

Product 2

Single Quad MS selectivity proportional to

spectral resolution

no selectivity against ions

with same m/z

Triple Quad MS Precursor selectivity same as MS but

high probability that one or more of the

product ions will be a unique dissociation

product of the precursor only

AND NOT the interference

Interference*

analyte

interference

unit mass resolution

*Because the concentrate of the matrix may be much greater than the analyte,

even matrix isotope ions (A+1, A+2, etc) may be a significant interference

As Matrix Increases - MS/MS is More Valuable

100 fg HCB in Clean Matrix 300 fg HCB in Diesel

Sin

gle

MS

: S

IM 2

83.8

M

S/

MS

: 283.8

:213.9

S/N=37:1 RMS

S/N=26:1 RMS

SIM about equal to MS/MS in clean matrix

MS/MS 15x better than SIM in complex matrix

Garlic: Single Quad SIM v.s. GC-QQQ

MRM

10 ppb Omethoate, MRM

Compound was confirmed easily

40 ppb Omethoate, SIM

Ion ratios were seriously distorted

GC-QQQ removes matrix interference and provides more reliable confirmation

Agilent Restricted

Page 23

240 Ion Trap GC/MS

• All Internal Ionization IT functionality • Liquid PCI, MS/MS, EI – all in one run

• Optional External Source • EI, PCI, NCI, Hybrid CI

• Higher performance scan function • Increased EI sensitivity

• Faster scanning (10K) for shorter cycle time

• Enhanced charge capacity

• MS/MS and MSn

7890A/240 Ion

Trap GC/MS

Agilent Restricted

Page 24

3D Ion Trap

Different ionization (EI and CI) and scanning options (Full scan, MS/MS and

SIS) can be utilized even in the same run to enhance both the qualitative and

quantitative information content of the results.

EI/MS

CI/MS

CI/MS/MS

EI/MS/MS

EI/SIS EI/MS

IT-MS Changing Modes During a Single Analysis Winning Benefits

7200 Series Q-TOF for GC/MS A new analytical tool for solving complex analytical problems

Badr Astiphan GC/MS Product Specialist

Mid America

= +

What is it? 7890 + 7000 + 6500 = 7200 GC/Q-TOF

Quadrupole Time of Flight MS

Time of Flight MS

Triple Quadrupole GC/MS

Merging two proven platforms

7000B TQ 6500 Q-TOF

NEW

Optics NEW

Removable

Ion Source

Two

300 L/s Turbos

Removable Ion Source (RIS)

Automated

Retractable

Transfer Line

RIS

Automated

Gate Valve

Jan.-Apr. 2009

Expert Tour

Page 30

Q-TOF Fundamentals

September, 2008 Page 30

Ion optics Common with Q & QQQ

Flight tube Common with TOF

Octopole 1

DC Quad

Collision cell Common with QQQ

Rough Pump

Turbo Turbo Turbo

Quad Mass Filter (Q1)

Collision Cell Lens 1 and 2

Octopole 2

Ion Pulser

Ion Mirror

Detector

Turbo

Two key concepts for TOF:

1. Exact Mass

2. Mass Error

How TOF Works

t0

V

t

3 simple equations:

𝐸 = 1

2𝑚𝑣 2

𝐸 = 𝑧 𝑉

𝑣 = 𝑑

(𝑡 − 𝑡0)

These combine to give the equation

for time-of-flight:

t = (m/z)1/2 * d / (2 * V)1/2 + t0

Which simplifies to the mass

relationship:

𝑚/𝑧 = 𝐴 (𝑡 – 𝑡0)2

Where A is an instrument design

constant

v

m/z

A Time of Flight “Scan”

Pulser Detector

1. Pulse ions every 100 microseconds (10E-6), 10kHz

2. Measure at detector each nanosecond (10E-9)

3. 100,000 data points in each transient

4. Sum 500 – 10000 transients into one scan

5. Produces spectra with excellent ion statistics

15 µsec – m/z 69

45 µsec - m/z 614

Mirror

Flight Tube

Resolving Power & Mass Accuracy

R = 614/0.68 = 903

Δmz = 0.1/614

= 160 ppm

Pw=0.68

Mz=614

SQ

TQ

IT

TOF

Q-TOF

R = 614/0.0423 = 14522

Δmz = 0.0004/613.96

= 0.7 ppm

Resolving Power:

R=mz/FWHM

Mass Accuracy: Δmz=dm/mz*106,

parts per million (ppm)

PFTBA mass 614

C12F24N=613.964203

1 Da.

1 Da.

240.1218

240.0785

Flurenol methyl ester

m/z = 240.0781

Mass error = 1.7 ppm

Dimetilan

m/z = 240.1217

Mass error = 0.4 ppm

~13,500 resolution FWHM

How Much “R” is Enough?

No IRM corrections applied

Dm = 0.043 Da.

How Much Accuracy is Needed?

1

10

100

1000

10000

0.1 1 10 100 1000

# P

oss

ible

Ch

emic

al F

orm

ula

s

mass uncertainty, ppm

Possible Number of Chemical Formulas at m/z 272

Formulas made of:

C,H,N,O,F, & Cl

mass uncertainty

ppm amu # of Possible

Formulas 1000 0.3 7657

368 0.1 4050 100 0.03 1223

37 0.01 466 10 0.003 120

4 0.001 43 1 0.0003 11

0.4 0.0001 5 0.1 0.00003 2

Octafluoronaphthalene

(CAS 313-72-4)

C10F8

271.986677420 amu

Accurate mass reduces risk of investing effort on the wrong molecule

MSD

TOF 4 ppm

1 ppm

35

Jan.-Apr. 2009

Expert Tour

Page 36

What does “Exact Mass” mean?

September, 2008 Page 36

Element Atomic Number Exact Mass

H 1 1.007825

C 6 12.000000

N 7 14.003074

O 8 15.994915 C15H10NO3ClI2 287.0349209 Clioxanide

C8H18NO4PS2 287.0414860 Vamidothion

C16H15N3F2Si 287.1234039 Flusilazol

C6H6Cl6 287.8600665 Lindane

C10H12N2O6S 288.0416000 Carbasulam

C9H21O2PS3 288.0441285 Terbufos

C13H21O3PS 288.0949000 Iprobenfos

C15H17N4Cl 288.1141743 Myclobutanil

C12H21N2O4P 288.1238937 Diazoxon

C11H20N4O3PS 288.1256000 Epronaz

C11H21N4O3P 288.1351000 Pirimetaphos

C16H20N2O3 288.1473925 Imazamethabenz

0.2874 amu

The Key for getting useful TOF results is good mass accuracy.

Mass Uncertainty Measurements

0.1

1

10

100

1 10 100 1,000 10,000 100,000 1,000,000

Mass u

nc

ert

ain

ty,

pp

m

Number of Ions Detected

37

Maximizing Accurate Mass - Internal Reference

Mass (IRM)

• Engineering goal: minimize source of drift

– Proprietary INVAR flight tube

– Electronics optimized

– Ion Beam Flattening

– IRM correction often not needed

• IRM ions may be an interference with analyte ions

• Proprietary IRM delivery system is “backup” correction

– “Locks” mass axis to known background ions

• Tris(pentafluoroethyl)-s-triazine

– “On the fly” mass axis correction

38

Comparing Quad & TOF Sensitivity

Orthogonal Acceleration

TOF will lose low mass

sensitivity compared to a

Quad instrument but gain at

the mid and high mass

range.

Sensitivity is generally

between that of SIM and

Scan on a SQ or MRM and

Product Ion Scan on a TQ

39

TIC

EIC 283.8096+/- 0.5 Da.

EIC 283.8096+/- 2 ppm (+/- 0.0005 Da.)

Hexachlorobenzene – 600 ppb in marine sediment extract

a

b

c

Target compound quantitation and confirmation

No matrix interference

• Good quantification

• Good confirmation

Background

200X smaller

Accurate mass Target compound quantitation

Hexachlorobenzene

1 ppb – 5000 ppb

EIC window +/- 20 ppm

R2 > 0.9979

Linear response > 5X103

Good quantification

Structure Elucidation

Nominal loss = 38 m/z

-H20, -HF

F

F

F F

F

F

F

F

F

OH2+

-F2

F

F

F F

F

F

F

OH2+

CH2+

F

F

F F

F

F

F F-H2O -HF

Exact Mass: 265.0269

Exact Mass: 38.0168Exact Mass: 227.0102

Exact Mass: 227.0301

C+

F

F

F F

F

F

F F

Exact Mass: 37.9968

Acronym Observed Base Peak m/z Molecular ion -F2 m/z Dppm Molecular ion -H20, -HF m/z Dppm

4:2 FTOH 227.0104 227.0301 86.7726 227.0102 -0.8810

MS/MS: When Resolution Is Not Enough?

• MS/MS product ions are generally well separated in mass

– Product ion masses do not shift due to lack of resolution

• Why use Q-TOF rather than triple quadrupole?

• Sometimes qualifier ions have low abundance

• Accurate mass measurement of quantitation ion offers more

confirmatory information than using a low abundance qualifier ion

MS/MS Chemical Noise Reduction BB1-1pg OFN in PFTBA Background

Evolution of GC/MS

Page 44

MS

m/z 272

54:1 S/N

MS/MS

272:222

216:1 S/N

Analyte

ions

Matrix ions Analyte ions with minimal

matrix ions

Q-TOF Example of Identification — Compound “B”

C16H14O4 (Rings + Double Bonds = 10)

Evolution of GC/MS

Page 45

(M – H)+

269.0802

Candidate

structures m/z

(experimental)

Formula Error

(ppm)

Score

269.0802 C16H13O4 2.2 80.7

193.0494 C10H9O4 0.6 96.7

167.0334 C8H7O4 3.0 N/A

166.0259 C8H6O4 0.6 N/A

138.0310 C7H6O3 1.1 98.1

110.0359 C6H6O2 3.0 N/A

95.0127 C5H3O2 0.9 99.5

– CH2=CH–C6H5

– CO

– CH3

– CO

– H

– C6H5

– CH=CH–C6H5

For the 5 candidate structures, only one fit the losses identified by

CID experiments on multiple precursor ions

Value of TOF and Q-TOF

• High resolution full scan spectra

• Higher selectivity without MS/MS

• > 12K versus < 1K for SQ (15-20X higher)

• Accurate mass measurements

• Better qualitative decisions (molecular formula information)

• < 5 ppm versus 350-400 for SQ (70-80X better)

• Fast acquisition of full spectra range

• With consistently greater sensitivity than SQ

• 50 Hz max versus typically < 5 Hz max for SQ

• MS/MS with Product Ion spectra

• More selective than TQ (due to higher resolution)

• With accurate mass information for each product ion

• Powerful structural elucidation tools

Ideal tools for solving complex analytical problems


Industry-standard

workhorse

Routine analyses

(environmental, food,

tox, pharmaceutical,

chemical, materials)

High-throughput,

targeted quantitative analyses

(food, drugs, environmental)

Highest speed & sensitivity;

New MassHunter SW

Ultimate combination of qualitative

and quantitative capability

Demanding analyses (R&D and routine)

(metabolomics, food, toxicology)

Industry-leading performance,

usability, reliability, and support

Routine to unknowns analysis

(academia, environmental, food)

Foundation:

Q-TOF

GC/MS

Triple Quad

GC/MS

Single Quad GC/MS

Ion Trap GC/MS Greater flexibility between

EI, CI, and MS/MS modes

Q&A Discussion

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