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© 2012 Sigma-Aldrich Co. All rights reserved.

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New Developments in Chromatography

at Supelco

L.M.SidiskyMay 19, 2015

ISCC, Fort Worth, TX

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© 2012 Sigma-Aldrich Co. All rights reserved.

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New Products

• GC

• SPME

© 2012 Sigma-Aldrich Co. All rights reserved.

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New Products

• GC

• SLB-35ms

• SLB-IL111 and SP-2560, 200 meter versions

• SLB-IL60 Fusel Alcohols Application

• SLB-IL D3606

• SLB-IL PAH

• Ionic Liquids for Water and Alcoholic Beverage Analysis

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New Products

• SLB-35ms

• A new line of 35% phenyl capillary columns with a

• maximum temperature of 350°°°°C

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SLB-IL111Phase Structure

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

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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

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Positional cis/trans FAME Isomerscolumn: SP-2560, 200 m x 0.25 mm I.D.,

0.20 µm oven: 180 °C isothermal

inj.: 250 °Cdet.: 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 isothermalinj.: 250 °C

det.: FID, 250 °C carrier gas: hydrogen, 1 mL/min.

injection: 1 µL, 100:1 splitliner: 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)

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SLB-IL60Phase Structure

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

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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

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Fusel Oils Separation-Active amyl alcohol (2-methyl-1-butanol) and Isoamyl

alcohol (3-methyl-1-butanol), 90ºC Isothermal

0 2 4 6

Time (min)

1.0 2.0 3.0 4.0 5.0 6.0

Time (min)

SLB-IL60 Supelcowax 10

2-methyl-1-butanol

3-methyl-1-butanol

Coelution

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0 2 4 6 8 10 12

Time (min)

0

200

400

600

800

1000

1200

1400

ethanol

benzene

toluene

MIBK

n-butanol

se

c-b

uta

no

ln

-pro

pa

nol

octane

iso

-bu

tano

l

Rs(ethanol/benzene)= 12.6Rs(MIBK/n-propanol)= 45Rs(toluene/isobutanol)= 5.6

SLB-IL D360660m 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)

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Reformulated Gasoline with D3606 Oxygenates

50 ºC (6 min) to 265 ºC (10 min) at 15 ºC/min.

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0 10 20

Time (min)

0

200

400

600

800

1000

1200

1400

1600

1800

1

23

47

8

9

10

11

12

13

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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

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column: SLB-5ms, 30 m x 0.25 mm I.D., 0.25 µm df (28471-U)oven: 80 ºC, 15 ºC/min to 250 ºC, 8 ºC/min to 325 ºC (15 min)inj. temp.: 300 ºCdetector: MSD, full scan, 45-500 m/z, 300 ºC interfacecarrier gas: helium, 1.2 mL/min constant flowinjection: 0.5 uL, splitless (1 min)liner: 4 mm I.D. FocusLinersample: EPA 610 PAH mix + Benzo[j]fluoranthene, diluted to 100 µg/mL in methylene chloride

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PAHs on a Traditional 5% Silphenylene Phase

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

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Selected Isomers

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Ionic Liquid Water Separations

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Column: SLB-IL 94, SLB-IL 107, IL 200 30m x 0.25mm x 0.20umdf

Oven: 35˚C, 4˚C/min to 125˚C, 125˚(2min)

Det: TCD, 300˚C

Flow Rate: 25cm/sec constant pressure He

Inj: 250˚C,1uL, split, 100:1

Liner: 4mm ID cup design split liner

Samples: IL Solvent Test Mix: MeOH, EtOH, Acetone, IPA, n-propanol, 1-butanol, 1,4-Dioxin

in water

NH

C5H10P+

O

N

HN C5H10

P+

OHN

C5H10

P+

O

S

N

S CF 3

CF 3

OO

OO

-3

(NTF 2-)

N

O

NNN

HOOH

O

O

O-S

O

O

F3CO-S

O

O

F3C

N NH3C

O

O O

N NCH3

+

+

F3C

S

O

O

O _

O

S

CF3

O

O_

SLB-IL 94

SLB-IL 107

IL 200

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IL Solvent Mix on SLB-IL 94 30m x 0.25mm x 0.20umdf

0 2 4 6 8 10 12 14

Time (min)

1

2

3

4

5

6,7,8,9

Figure 9. Solvent test standard programmed separation on SLB-IL 94; 1) MeOH, 2) MeCl23) acetone, 4) ethanol, 5) IPA, 6) n-Propanol, 7) 1,4dioxane, 8) butanol9) water

© 2012 Sigma-Aldrich Co. All rights reserved.

IL Solvent Mix on SLB-IL 107 30m x 0.25mm x 0.20umdf

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0 2 4 6 8 10 12 14

Time (min)

1

2 3

4,5

6,7

9

8

Figure 8. Solvent test standard programmed separation on SLB-IL 107; 1) MeCl2, 2) acetone, 3) IPA, 4) ethanol, 5)methanol, 6) n-Propanol, 7) 1,4dioxane8) butanol, 9) water

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SLB-IL 107 SPME Fiber Test STD

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10 20

Time (min)

Figure 1. Temperature programmed run for SPME Fiber Test Standard on SLB-IL 107. 1uL injection of standard withvaried concentrations (10-200ppm) at 100:1 split. Standard is prepared in water.

1. Acetone2. IPA3. EtOH/MeOH4. N-propanol/1,4-Dioxane5. Butanol6. H2O

1

2

3

4

5

6

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C1-C6 Alcohol Mix

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10 20

Time (min)

1. Isopropanol2. Ethanol3. Methanol4. 2-Butanol5. n-Propanol6. Isobutanol7. n-Butanol8. Isoamyl alcohol9. Pentanol10. Cylcohexanol

2,3

4

5 6

7 8

9

10

H2O

Figure 2. Temperature programmed run for light alcohol mix on SLB-IL 107. 1uL injection of a 500ug/mL sample at 100:1 split. Note the sample has adsorbed some water in storage.

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Grappa Bassano

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10 20

Time (min)

Figure 4. Temperature programmed run for Grappa Bassano on SLB-IL 107. . SPME Carboxen extraction. Selectedpeaks with high confidence of identification.

EtOH

H2O

furfural

C4-OH’sC5-OH’s

Silane impurity

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Grappino

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10 20

Time (min)

EtOH

C4-OH’s

C5-OH’s

H2O

furfural

Figure5. Temperature programmed run for Grappino on SLB-IL 107. . SPME Carboxen extraction. Selectedpeaks with high confidence of identification.

© 2012 Sigma-Aldrich Co. All rights reserved.

Tito’s Vodka

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10 20

Time (min)

Figure6. Temperature programmed run for Tito’s Vodka on SLB-IL 107. . SPME Carboxen extraction. Selectedpeaks with high confidence of identification.

EtOH

H2O

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Ouzo

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0 10 20 30

Time (min)

EtOH

H2O

P-anisole

Aromatic derivatives

Phthalates and FAMEs

Figure9. Temperature programmed run for Ouzo on SLB-IL 107. . SPME Carboxen extraction. Selectedpeaks with high confidence of identification.

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Over-coated PDMS/ DVB SPME Fibers

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Purpose for Over-coating Adsorbent Fibers

1. PDMS over-coating is intended to extend fiber life when fibers are immersed in the matrix solution.

2. Matrix components such as sugars tend to stick to adsorbent coating coatings that reduces fiber life.

3. PDMS coating serves as a barrier to the matrix. The matrix components tend not to stick to PDMS.

4. Analytes tend to migrate through the PDMS coating onto the adsorbent surface or into the pores where they are more tightly retained.

5. Over-coating application seals the ends of the fiber so that matrix does not wick into solution.

6. Fibers are more durable.

7. Less background in chromatograms

8. Reduces matrix competition with analytes

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Coating Modification Optimization

� Over-coating standard PDMS/DVB with a PDMS

Microphotographs of a standard PDMS/DVB fiber and the same fiber coated with an external PDMS layer.

PDMS over-coating

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E. A. Souza-Silva, J. Pawliszyn, Anal. Chem. 84 (2012), 6933-6938.

© 2012 Sigma-Aldrich Co. All rights reserved.

SEM of Cross Section PDMS-DVB Fiber with 30µm

PDMS Overcoat

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