innovations in gc and gc-ms - sigma-aldrich · 2020. 10. 24. · watercol” series of ionic liquid...

Only to be used in USA & Canada, never outside these two countries“

MilliporeSigma is a business of Merck KGaA, Darmstadt, Germany

Len Sidisky June 2, 2016, Riva del Garda, Italy

ISCC 2016

INNOVATIONS IN GC & GC-MS

2 Title of Presentation| DD.MM.YYYY

Overview of Ionic Liquids

New Ionic Liquid Column Developments

Watercol™ Series

SLB® IL (i-series)

SLB® ILPAH

SLB® ILD3606

200 m SP™ 2560 and SLB® IL111

Other Developments

SLB® 35ms

Agenda

3

Ionic Liquids

Ionic liquids - a class of ionic solvents with low melting points

Unique combination of cations and anions that can provide different selectivities when used as stationary phases in GC

Numerous combinations of cations and anions are possible allowing for “tailored” selectivity, application or function

4

Desirable IL Properties for GC Use

Several properties make ILs desirable as GC stationary phases

remain liquid over a wide temperature range (Room Temperature350 o+C)

very low volatility

highly polar nature

broadest range of solvation interactions of any known solvent

good thermal stability

high viscosity

easily tailored to provide different polarities/selectivities

5

Solvation Parameter Model (SPM) Data

Only the ionic liquids are capable of simultaneously providing:

Intense H-acceptor interactions

(a constant)

Intense H-donor interactions

(b constant)

Dipolar interactions (s constant)

p-p interactions (e constant)

Limited dispersive interactions

(l constant)

•Line 1: Poly(trifluoropropyl)siloxane

•Line 2: Poly(phenyl)siloxane

•Line 3: Poly(cyanopropyl)siloxane

•Cluster I: Polyethylene glycol

•Cluster II: Ionic liquid

95 probes / 52 columns

Ref: Supelco Reporter 33.1 (March 2015), page 3-4.

Courtesy of Rosa Lebrón-Aguilar, CSIS, Madrid, Spain

Principle Component Analysis (PCA) of

Polarity vs. Selectivity

6

Geminal Dicationic Ionic Liquid Stationary Phase

SLB-IL100

1,9-di(3-vinyl-imidazolium) nonane bis(trifluoromethyl) sulfonyl imidate

+ +NN NN

C9 spacer vinyl moiety imidazolium cation

bis(trifluoromethyl) sulfonyl imidate anion

imidazolium cation

7

SLB-IL76 Phase Structure

sigma-aldrich.com/il-gc

Tri(tripropylphosphoniumhexanamido)triethylamine bis(trifluoromethylsulfonyl)imide

8



1,5-Di(2,3-dimethylimidazolium)pentane bis(trifluoromethylsulfonyl)imide

GC Column Polarity Scale Visual Representation

9

10

Fusel Alcohols; 90 ºC Isothermal

0 2 4 6

Time (min)

1.0 2.0 3.0 4.0 5.0 6.0

Time (min)

SLB-IL60 30 m x 0.25 mm I.D., 0.20 µm

PEG 30 m x 0.25 mm I.D., 0.25 µm

1

2 1,2

1. 2-Methyl-1-Butanol (Active Amyl Alcohol) 2. 3-Methyl-1-Butanol (Isoamyl Alcohol)

11

Anilines; 75 ºC (2 min), 10 ºC/min to 250 ºC

11.0 12.0 13.0

12.0 13.0 14.0

1. Aniline 2. 3-(Chloromethyl)pyridine 3. 2-Aminotoluene 4. 4-Aminotoluene 5. 3-Aminotoluene 6. 2,6-Dimethylaniline 7. 2,4-Dimethylaniline

SLB-IL59 30 m x 0.25 mm I.D., 0.20 µm

PEG 30 m x 0.25 mm I.D., 0.25 µm

7 6

5 4 3

2

1

7 6

5 4 3

2

1

12.0

12

Aromatics in Reformulated Gasoline; Last Analyte to Elute is 1-Methylnaphthalene (1mN)

TCEP (1mN elutes at 39.4 min) 60 m x 0.25 mm I.D., 0.44 µm

SLB-IL111 (1mN elutes at 14.7 min) 60 m x 0.25 mm I.D., 0.20 µm

B

13

Native Spearmint Essential Oil; 75 ºC (4 min), 4 ºC/min to 200 ºC (10 min)

SLB-IL60 30 m x 0.25 mm I.D., 0.20 µm

PEG 30 m x 0.25 mm I.D., 0.25 µm

0 10 20 30 40

Time (min)

0 10 20 30

Time (min)

14

Cis/ trans FAMES on SLB-IL60 vs. PEG Type Phase

11.0 12.0 13.0 14.0 15.0Time (min)

trans cis

C18:1n9 cis / trans FAMEs @ 180°C

SLB IL60

21.0 22.0 23.0 24.0Time (min)

PEG

C18:2n6 cis & trans FAME Isomers- 180°C

10 12 14 16 18 20Time (min)

C18:2n6 tt

C18:2n6 cc

26 28 30 32 34Time (min)

C18:2n6 tt

C18:2n6 cc

15

Watercol™ Series

Watercol” series of ionic liquid capillary GC columns are characterized by their ability to produce a sharp peak shape for water and other small polar analytes. The water peak shape is sharp enough so that:

Water can be integrated and quantified

Water does not interfere chromatographically with many other small polar analytes

Three different chemistries:

WatercolTM1460, WatercolTM1900, and WatercolTM1910

16

Watercol™ Series

WatercolTM1460

WatercolTM1900

WatercolTM1910

17

WatercolTM Selectivity Comparison

0 2 4 6 8 10 12

Time (min)

0 2 4 6 8 10 12

Time (min)

0 2 4 6 8 10 12

Time (min)

H2O

H2O

H2O

WatercolTM1460

WatercolTM1900

WatercolTM 1910

18

Polarity Comparison- Water as the Injection Solvent

WatercolTM1460

WatercolTM1900

WatercolTM1910

19

Column Durability- Repeat Water Injections WatercolTM1460

1st Analysis

50th Analysis

100th Analysis

0 2 4 6 8 10 12 14

Time (min)

0 2 4 6 8 10 12 14

Time (min)

20

Water Calibration Curve (0.05-1%) on WatercolTM1460

21

Water Standard (0.25% in Ethanol) on WatercolTM1460

0 2 4 6 8 10 12 14

Time (min)

0 2 4 6 8 10 12 14

Time (min)

FID

TCD

22

Water Calibration Curve (0.01-0.5%) on WatercolTM1910

23

Water Standards on WatercolTM1910

0 2 4 6 8

Time (min)

0 2 4 6 8

Time (min)

0.05% Standard

0.5% Standard

24

Unleaded gasoline spiked with Water- WatercolTM1910

0 2 4 6 8 10 12 14

Time (min)

0 2 4 6 8 10 12 14

Time (min)

2

Spiked

FID

Spiked

TCD

1. Ethanol

2. Water

1

1 2

25

60-Component Solvent Mix on WatercolTM1910

6 8 10

0 10 20 30

Time (min)

6 8 10

0 10 20 30

Time (min)

FID

TCD

1

1

26

Tequila on WatercolTM1910

0 2 4 6 8 10

Time (min)

0 2 4 6 8 10

Time (min)

Tequila

FID

Tequila

TCD

Ethyl acetate Ethanol n-Propanol Isobutanol Active amyl alcohol Isoamyl alcohol Water

GC-VUV Water Analysis Method: Watercol 1900

0.00

0.10

0.20

0.30

0.40

0.50

0 2 4 6

VU

V A

bso

rba

nce

Time (Minutes)

Oxygen

DCM

EtO

H

Wate

r

Parameter Setting

Inj. Temp 250 C

Split

Ratio 5

Column

Flow

He, 3

mL/min.

Inj. Vol. 0.5 uL

Makeup

Gas

Pressure

N2

0.25 psi

Flow Cell

Temp 275 C

Data Acq.

Rate 4.5 Hz

Robust Water Separation with Watercol 1900

VUV Analytics- Lindsey Shear

0.00

0.02

0.04

0.06

0.08

0.10

0 2 4 6

VU

V A

bso

rba

nce

Time (Minutes)

H2O in DCM

* 120 ppm

0.00

0.10

0.20

0.30

0.40

0.50

0 2 4 6

VU

V A

bso

rba

nce

Time (Minutes)

H2O in ETOH * 3000 ppm

0.00

0.02

0.04

0.06

0.08

0.10

0 2 4 6

VU

V A

bso

rba

nce

Time (Minutes)

H2O in MEOH

* 170 ppm

0.00

0.02

0.04

0.06

0.08

0.10

0 2 4 6

VU

V A

bso

rba

nce

Time (Minutes)

H2O in ETOAC

* 130 ppm

Robust Water Separation with Watercol 1900

VUV Analytics- Lindsey Shear

0.00

0.02

0.04

0.06

0.08

0 2 4 6

VU

V A

bso

rba

nce

Time (Minutes)

H2O in n-Hexane

* 100 ppm

0.00

0.20

0.40

0.60

0.80

1.00

0 2 4 6

VU

V A

bso

rba

nce

Time (Minutes)

H2O in CH3CN * 6300 ppm

0.00

0.02

0.04

0.06

0.08

0.10

0 5

VU

V A

bso

rba

nce

Time (Minutes)

H2O in IPA

* 270 ppm

0.00

0.10

0.20

0.30

0.40

0.50

0 5

VU

V A

bso

rba

nce

Time (Minutes)

H2O in Cyclohexanone

2000 ppm *

Water Determination: Linearity VUV

y = 0.00000659x + 0.00452439

R² = 0.99865048 0

0.005

0.01

0.015

0.02

0.025

0.03

0.035

-1000 0 1000200030004000

Response (

AU

)

Concentration Added (ppm)

H2O in ETOH

y = 0.00000559x + 0.00325845 R² = 0.99915671

0

0.005

0.01

0.015

0.02

0.025

0.03

-1000 0 1000 2000 3000 4000

Res

po

nse

(A

U)


H2O in CH3CN

y = 0.00000655x + 0.00607548 R² = 0.99309614

0.00

0.01

0.02

0.03

0.04

-1000 0 1000 2000 3000 4000

Res

po

nse

(A

U)


H2O in MEOH

y = 0.00000573x + 0.00092285 R² = 0.99922388

0.00

0.01

0.02

0.03

-1000 0 1000 2000 3000 4000

Res

po

nse

(A

U)


H2O in Cyclohexanone

Reproducibility and Detection Limits VUV

0.00

0.01

0.02

0.03

0.04

0.05

4.60 4.80 5.00

VU

V A

bso

rba

nce

Retention Time (Minutes)

H2O in Dry DCM Parameter Setting Unit

Average

Area 0.00187 AU

% RSD 4.68 -

Conc.

Backgrou

nd

100 ppm

MDL 13 ppm

Average

Height 0.035 AU

RMS

Noise .00029 AU

S/N 120 -

LOD 2.5 ppm

A B

Water Content in Specialty Chemicals VUV

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

4.70 4.90 5.10

VU

V A

bso

rba

nce

Retention Time (Minutes)

0

32

64

128

256

511

1022

Added H2O Concentration (ppm)

B

0

50

100

150

200

250

Co

nce

ntr

atio

n (

pp

m)

Cyclohexanone A

Cyclohexanone B

A

33

SLB® IL (i-series)

SLB IL60i SLB IL76i SLB IL111i

34

Resolution of Active Amyl Alcohol and Isoamyl Alcohol

1.0 2.0 3.0

Time (min)

1.0 2.0 3.0

Time (min)

1.0 2.0 3.0

Time (min)

SLB IL60i

SLB IL76i

SLB IL111i

C11

C15

C13

35

SLB IL60i Phase Structure


1,12-Di(tripropylphosphonium)dodecane bis(trifluoromethylsulfonyl)imide

Residual solvents - Class IIB

0 10 20 30 40 50

Time (min)

8

10

12

14

16

18

20

22 SLB IL60i

0 10 20 30 40 50

Time (min)

4

6

8

10

12

14

16

18

20

SLB IL60

1

2 3

4

5

6

7

8

DMSO

7

8

DMSO 1

2 3 4 5 6

Residual solvents - Class IIC

0 10 20 30 40 50

Time (min)

20

40

60

80

100

SLB IL60i

0 10 20 30 40 50

Time (min)

20

40

60

80

100

SLB IL60

1 2

3

4

5

6

1 2

3 4

5

6

7

8

DMSO

7

8

DMSO

0 10 20

Time (min)

20

40

60

80

100

120

140

0 10 20

Time (min)

20

40

60

80

100

120

140

160

180

200

Comparison between SLB IL60 and SLB IL-60i

1

2

3

4

5

6 7

8 9

1

2

3

4

5

6

7

8 9

SLB IL-60i 30m x 0.25 mm I.D. x 0.20 um df.

SLB IL-60 30m x 0.25 mm I.D. x 0.20 um df.

Components: 1. 2-octanone 2. n-pentadecane 3. 1-octanol 4. n-hexadecane 5. n-heptadecane 6. n-octadecane 7. 2,6-dimethylphenol 8. 2,6-dimethylaniline 9. n-eicosane

Conditions: Sample: polar test mix Oven: 130 °C Carrier gas: Helium @ 1.2 mL/min Injection: 1 µL (250 °C, split 100:1) Detector: FID (260 °C) * n-eicosane peak is slightly overloaded in both chromatograms

G. Serrano (21/01/15)

0 10 20

Time (min)

20

40

60

80

100

0.0 1.0 2.0 3.0 4.0 5.0

Time (min)

20

40

60

80

6.0 7.0 8.0 9.0 10.0 11.0

Time (min)

20

40

60

80

12 14 16 18 20 22

Time (min)

20

40

60

80

56 solvents-composite mix

Instrument: GC-FID

Inj. Temp.: 250 °C

Det. Temp.: 250°C

Oven: 40°C (4 min.), 8 °C/min. to 200°C (5 min.)

Carrier gas: Helium, constant pressure

Injection type: Auto

Injection volume: 1 uL, split 100:1

Sample: various 0.2% v/v in pentane

Liner: 4 mm ID focus Liner

Wash solvent: pentane

1 2

3

4

5

6

7

8 9

10 11

12 13

14 16 17

18

19

15

20

21

22 23

24

25

26

32

29

31

28

33 36

34

35

30

38

37 39 41

42 27

43

40

44

45

46

47

48

49 50

51

52 53

SLB IL-60 30m x 0.25 mm I.D. x 0.20 um df.

0 10 20

Time (min)

20

40

60

80

100

0.0 1.0 2.0 3.0 4.0 5.0

Time (min)

20

40

60

80

100

5.0 6.0 7.0 8.0 9.0 10.0 11.0

Time (min)

20

40

60

80

100

12 14 16 18 20 22

Time (min)

20

40

60

80

100

56 solvents-composite mix

Instrument: GC-FID

Inj. Temp.: 250 °C

Det. Temp.: 250°C

Oven: 40°C (4 min.), 8 °C/min. to 200°C (5 min.)

Carrier gas: Helium, constant pressure

Injection type: Auto

Injection volume: 1 uL, split 100:1

Sample: various 0.2% v/v in pentane

Liner: 4 mm ID focus Liner

Wash solvent: pentane

1

2

3

4

5

6 7

8

9

10 11

12

13 14 16 17

18

19

15

20 21

22 23

24 25

26

27

28

6

30

32

29 40

41

36

43

42

44

45

35

39

37

38

31

34

33

46

52

54

47

50 55

48

53

51

49

SLB IL-60i 30m x 0.25 mm I.D. x 0.20 um df.

41



Tri(tripropylphosphoniumhexanamido)triethylamine bis(trifluoromethylsulfonyl)imide

42

Polar Test Mix Analysis

sigma-aldrich.com/gc

0 10 20

Time (min)

0

10

20

30

0 10 20

Time (min)

20

40

60

80

1

2

5

3,4

8

76

109

1

2

5

3

8

7

610

9

(a)

(b)

4

SLB IL76i

SLB IL76

43

C1-C12 Alcohols Analysis

sigma-aldrich.com/gc

0 2 4 6 8 10 12 14 16 18

Time (min)

0

2

4

6

8

10

0 10 20

Time (min)

10

20

C1

C2 C5C3C8C7C6

C11C9

C4

C10 C12

C1

C2C5C3

C8C7C6

C11C9

C4

C10 C12

(a)

(b)

SLB IL76i

SLB IL76

0 10 20 30 40 50

Time (min)

6.0

7.0

8.0 SLB IL76i

Residual solvents - Class IIB

1

2 3

4 5

6

7 8

DMSO

Conditions: Column: SLB IL76i, 30m x 0.25 mm I.D. x 0.20 µm df. Oven: 35 °C (15 min), 5 °C/min to 200 °C Carrier gas: Helium @ 1.2 mL/min Injection: 1 µL (250 °C, split 100:1) Detector: FID (250 °C)

Components: 1. Chloroform 2. 1,2-Dimethoxyethane 3. Hexane 4. 3-Methyl-2-Pentanone 5. Nitromethane 6. Pyridine 7. Tetralin 8. Trichloroethylene

0 10 20 30 40 50

Time (min)

10

20

30

SLB IL76i

Residual solvents - Class IIC

1 2

3

4

5 6

7

8

DMSO

Conditions: Column: SLB IL76i, 30m x 0.25 mm I.D. x 0.20 µm df. Oven: 35 °C (15 min), 5 °C/min to 200 °C Carrier gas: Helium @ 1.2 mL/min Injection: 1 µL (250 °C, split 100:1) Detector: FID (250 °C)

Components: 1. N,N-Dimethylacetamide 2. N,N-

Dimethylformamide 3. 2-Ethoxyethanol 4. Ethylene gylcol 5. Formamide 6. 2-Methoxyethanol 7. N-Methylpyrrolidone 8. Sulfolane

46



1,5-Di(2,3-dimethylimidazolium)pentane bis(trifluoromethylsulfonyl)imide

47

C1-C12 Alcohols

0 2 4 6 8 10

Time (min)

20

40

60

80

100

7

6

9

5

8

1011 12

4

3

2

1

IL-1111911-84-02C1-C12 alcohols mix

0 2 4 6 8 10

Time (min)

20

40

60

80

100

76

9

58

10

1112

4

3

21

IL-110 (IL-111 wax)1928-14-05C1-C12 alcohols mix

(a)

(b)

SLB-IL111

SLB-IL111i

48

SLB® ILPAH Columns

49

PAH Separation on a Traditional 5% Silphenylene Phase

1. Naphthalene

2. Acenapthene

3. Acenaphthalene

4. Fluorene

5. Phenanthrene

6. Anthracene

7. Fluoranthrene

8. Pyrene

0 10 20 30

Time (min)

1

2

3 4 5,6

7 8

9,10 11,12,13

14

15,16

17

column: SLB® 5ms, 30 m x 0.25 mm I.D. x 0.25 µm df (28471-U) oven: 80 C, 15 C/min to 250 C, 8 C/min to 325 C (15 min)

det.: MSD, full scan, 45-500 m/z, 300 C interface

flow rate: He carrier gas, 1.2 mL/min, constant flow

liner: 4 mm I.D. FocusLiner™

sample: EPA 610 PAH mix + benzo(j)fluoranthene, diluted to 100 µg/mL in methylene chloride

9. Benzo(a)anthracene 10. Chrysene 11. Benzo(b)fluoranthene 12. Benzo(k)fluoranthene 13. Benzo(j)fluoranthene 14. Benzo(a)pyrene 15. Dibenz(a,h)anthracene 16. Indeno(1,2,3-cd)pyrene 17. Benzo(ghi)pyrene

50

Coelutions with Typical 5% Phenyl Selectivity

18.0 19.0

Time (min)

0 10 20 30

Time (min)

20.1 20.3 20.5 20.7 20.9 21.0 21.1

Time (min)23.6 23.8 24.0 24.2 24.4

Time (min)

Benzo(a)anthracene/Chrysene Dibenzo(a,h)pyrene/Indeno (1,2,3-cd)pyrene Benzofluoranthenes (b,k,j)

51

PAHs on SLB-ILPAH, 20 m x 0.18 mm I.D., 0.05 µm df

52

6.20 6.30

Time (min)

9.00 9.10 9.20

Time (min)

10.60 10.70 10.80 10.90 11.00

Time (min)

Selected Isomers

Anthracene/Phenanthrene Benzofluoranthenes

B

J K

Benzo(a)anthracene/Chrysene

9.00 9.10 9.20 9.30

Time (min)

Triphenylene/Chrysene

9.10 9.20 9.30 9.40 9.50

Time (min)

Cyclopenta(cd)pyrene/Chrysene

DIA: Can you put these with the chromatogram in Figure 7 ??

53

SLB® ILD3606 Columns

0 2 4 6 8 10 12

Time (min)

0

200

400

600

800

1000

1200

1400

ethanol

benzene

toluene

MIBK

n-butanol

sec-b

uta

nol

n-p

ropanol

octane

iso-b

uta

nol

Rs(ethanol/benzene)= 12.6

Rs(MIBK/n-propanol)= 45

Rs(toluene/isobutanol)= 5.6

SLB® ILD3606 60m x 0.25 mm ID x 0.20 µm df

• Specially prepared and tested ionic liquid column meets the requirements for resolving benzene and toluene from alcohol interferences (i.e. ethanol, butanol)

55

Reformulated Gasoline with D3606 Oxygenates 50 ºC (6 min) to 265 ºC (10 min) at 15 ºC/min.

0 10 20

Time (min)

0

200

400

600

800

1000

1200

1400

1600

1800

1

2 3

4 7

8

9

10

11

12

13

14

1.Methyl tert-butyl ether (MTBE) 8. toluene 2.tert-Amyl butyl ether (TAME) 9. n-butanol 3. Ethanol 10. ethyl benzene 4. Benzene 11. methyl iso-butyl ketone (MIBK 5. sec-butanol 12. p-xylene 6. n-propanol 13. m-xylene 7. iso-butanol 14. o-xylene.

5 6

56

200 m SP™ 2560 and SLB® IL111

57


C18:1 cis/trans FAME Isomers in Partially Hydrogenated Vegetable Oil (PHVO) SLB-IL111 vs. SP-2560: 100 m columns

SLB-IL111: Increased retention of cis relative to trans

complimentary selectivity

58

Positional cis/trans FAME Isomers

column: SP-2560, 200 m x 0.25 mm I.D.,

0.20 µm

oven: 180 °C isothermal inj.: 250 °C det.: FID, 250 °C carrier gas: hydrogen, 1 mL/min.

injection: 1 µL, 100:1 split

liner: 4 mm I.D., split liner with cup (2051001)

column: SLB-IL111, 200 m x 0.25 mm I.D.,

0.20 µm

oven: 168 °C isothermal inj.: 250 °C det.: FID, 250 °C carrier gas: hydrogen, 1 mL/min.

injection: 1 µL, 100:1 split

liner: 4 mm I.D., split liner with cup (2051001)

27.0 28.0 29.0 30.0 31.0 32.0

Time (min)

PHVO total FAMEs

20 22

Time (min)

PHVO total FAMEs

PHVO total FAMEs on SLB-IL111 @ 150 °C

isothermal

30.0 31.0 32.0 33.0 34.0 35.0

Time (min)

59

Analysis of C18:0, C18:1, C18:2, and C18:3 FAME Isomers on SP-2560 (200 m x 0.25 mm I.D.;

Isothermal Analysis)

60

Analysis of C18:0, C18:1, C18:2, and C18:3 FAME Isomers on SLB-IL111 (200 m x 0.25 mm I.D.;

Isothermal Analysis)

61

Peak IDs- C18:0, C18:1, C18:2, and C18:3 FAME Isomers

Peak IDs

1. C18:0 15. C18:1Δ6c 29. C18:2Δ9t,12c

2. C18:1Δ4t 16. C18:1Δ7c 30. C18:2Δ9c,12c

3. C18:1Δ5t 17. C18:1Δ8c 31. C18:3Δ9t,12t,15t

4. C18:1Δ6t 18. C18:1Δ15t 32. C18:3Δ9t,12t,15c

5. C18:1Δ7t 19. C18:1Δ9c 33. C18:3Δ9t,12c,15t

6. C18:1Δ8t 20. C18:1Δ10c 34. C18:3Δ9c,12c,15t

7. C18:1Δ4c 21. C18:1Δ11c 35. C18:3Δ9c,12t,15t

8. C18:1Δ5c 22. C18:1Δ12c 36. C18:3Δ9c,12t,15c

9. C18:1Δ9t 23. C18:1Δ13c 37. C18:3Δ9t,12c,15c

10. C18:1Δ10t 24. C18:1Δ16t 38. C18:3Δ9c,12c,15c

11. C18:1Δ11t 25. C18:1Δ14c

12. C18:1Δ12t 26. C18:1Δ15c

13. C18:1Δ13t 27. C18:2Δ9t,12t

14. C18:1Δ14t 28. C18:2Δ9c,12t

62

Conjugated Linoleic Acid (CLA) FAME Isomers on SP-2560 (200 m x 0.25 mm I.D.; Isothermal Analysis)

1. Methyl 9-trans,11-trans octadecadienoate 2. Methyl 9-trans,11-cis octadecadienoate 3. Methyl 9-cis,11-cis octadecadienoate 4. Methyl 10-cis,12-trans octadecadienoate

63

Conjugated Linoleic Acid (CLA) FAME Isomers on SLB-IL111 (200 m x 0.25 mm I.D.; Isothermal Analysis)

1. Methyl 9-trans,11-trans octadecadienoate 2. Methyl 9-trans,11-cis octadecadienoate 3. Methyl 9-cis,11-cis octadecadienoate 4. Methyl 10-cis,12-trans octadecadienoate

64

Rapeseed Oil FAME Isomers and Conjugated Linoleic Acid (CLA) FAME Isomers on SP-2560 (200 m x 0.25

mm I.D.; Isothermal Analysis)

1. C14:0 13. C22:0 2. C16:0 14. C22:1 3. C18:0 15. C24:0 4. C18:1n9c 5. Methyl 9-trans,11-trans octadecadienoate 6. Methyl 9-trans,11-cis octadecadienoate 7. Methyl 9-cis,11-cis octadecadienoate 8. C18:2n6 9. Methyl 10-cis,12-trans octadecadienoate 10. C18:3n3 11. C20:0 12. C20:1

65

Rapeseed Oil FAME Isomers and Conjugated Linoleic Acid (CLA) FAME Isomers on SLB-IL111 (200 m x

0.25 mm I.D.; Isothermal Analysis)

1. C14:0 13. C22:0 2. C16:0 14. C22:1 3. C18:0 15. C24:0 4. C18:1n9c 5. Methyl 9-trans,11-trans octadecadienoate 6. Methyl 9-trans,11-cis octadecadienoate 7. Methyl 9-cis,11-cis octadecadienoate 8. C18:2n6 9. Methyl 10-cis,12-trans octadecadienoate 10. C18:3n3 11. C20:0 12. C20:1

66

SLB® 35ms Intermediate Polar MS-Grade; Pesticides, PAHs,

Triglycerides, and Other Uses

MS-Grade columns are designed for GC and GC/MS analysts and provide

• low bleed

• inert

• durable

• low detection limits

• easy mass spectral identification

• Less instrument downtime

• good resolution

• short analysis times

• long column life

Organochlorine Pesticides

67

10 12 14 16 18Time (min)

1

’

2

3

4

5

6

7

8 9 10

14 12

13

20

21

11

16

17

18 19

22

15

10 12 14 16 18 20Time (min)

1

’

2

4

3

6

5

7

8

9 11

10

12 13

14

15 16

18

17

19

20

21

22

1. 2,4,5,6-tetrachloro-m-xylene 2. α-BHC 3. β-BHC 4. γ-BHC (Lindane) 5. δ-BHC 6. Heptachlor 7. Aldrin 8. Heptachlor epoxide 9. γ-chlordane 10. Endosulfan I 11. α-chlordane 12. 4,4’-DDE 13. Dieldrin 14. Endrin 15. 4,4’-DDD 16. Endosulfan II 17. Endrin aldehyde 18. 4,4’-DDT 19. Endosulfan sulfate 20. Methoxychlor 21. Endrin ketone 22. Decachlorobiphenyl

Oven: 100 °C (2 min.), 15°C/min. to 340°C (5 min.) Inj. Temp: 250°C Carrier gas: helium, 0.9 mL/min, constant flow Detector: µ-ECD 340 Injection: 1.0µL, splitless (0.75 min) Liner: 4 mm ID FocusLiner w/taper

SLB-5ms

SLB-35ms

68

PAHs in Soybean Oil (10 ng/g) – SLB 35ms

4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00

5000

10000

15000

20000

25000

30000

35000

40000

45000

50000

55000

60000

Time-->

Abundance

TIC: 0820026.D\data.ms

Soybean oil spike 1

2

3

4

5

6

7 8

9 10

11 12

13

14 15

I 16

Column: SLB-35 ms : 30 m x 0.25 mm I.D. x 0.25µm MS Temps: interface = 330 °C, source=250°C, quads = 200 °C Inj. Temp.: 300 °C Oven: 60 °C (1 min.), 20 °C/min. to 340 °C (10 min.) Carrier: helium, 1 mL/ml constant flow Injection: 0.5 µL pulsed splitless (60 psi/0.75 min), splitter open at 0.75 min. Liner: 2 mm ID focus liner w/taper

Peak List

1. Naphthalene

2. Acenaphthylene

3. Acenaphthene

4. Fluorene

5. Phenanthrene

6. Anthracene

7. Fluoranthene

8. Pyrene

9. Benzo[a]anthracene

10. Chrysene

11. Benzo[b]fluoranthene

12. Benzo[k]fluoranthene

13. Benzo[a]pyrene

14. Indeno[1,2,3-cd]pyrene

15. Dibenzo[a,h]anthracene

16. Benzo[g,h,i]perylene

IS: Benzo[b]chrysene

69

Butter Triglycerides- SLB 35ms 10 m x 0.25 mm I.D. x 0.10 µm

10 20

Time (min)

T42

GCxGC Analysis of Allergens in Perfume

70

SLB 5ms, 20 m x 0.18 mm I.D., 0.18 µm

SLB 3

5m

s, 5 m

× 0

.25 m

m I

.D., 0

.25 µ

m

71

Summary

Something totally new and completely different in the world of GC phases

Have the opportunity to impact current GC and GC-MS practices along several paths

New Ionic Liquid Column Developments

Watercol™ Series

Watercol 1460 Watercol 1900 Watercol 1910

SLB® IL (i-series)

SLB IL60i SLB IL76i SLB IL111i

SLB® ILPAH

SLB® ILD3606

200 m SP™ 2560 and SLB® IL111

SLB® 35ms

72

Acknowledgements Prof. Daniel Armstrong, U. Texas Arlington

Prof. Luigi Mondello, U. Messina, Messina, Italy

Dr. Pierluigi Delmonte, US FDA

Supelco R&D Team

Our customers worldwide

73


Thank You

innovations in gc and gc-ms - sigma-aldrich · 2020. 10. 24. · watercol” series of ionic liquid...

Documents