© 2012 Sigma-Aldrich Co. All rights reserved.
sigma-aldrich.com/analytical
New Developments in Chromatography
at Supelco
L.M.SidiskyMay 19, 2015
ISCC, Fort Worth, TX
1
© 2012 Sigma-Aldrich Co. All rights reserved.
2
New Products
• GC
• SPME
© 2012 Sigma-Aldrich Co. All rights reserved.
3
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
© 2012 Sigma-Aldrich Co. All rights reserved.
4
New Products
• SLB-35ms
• A new line of 35% phenyl capillary columns with a
• maximum temperature of 350°°°°C
© 2012 Sigma-Aldrich Co. All rights reserved.
5
SLB-IL111Phase Structure
sigma-aldrich.com/il-gc
1,5-Di(2,3-dimethylimidazolium)pentane bis(trifluoromethylsulfonyl)imide
© 2012 Sigma-Aldrich Co. All rights reserved.
6
sigma-aldrich.com/il-gc
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
© 2012 Sigma-Aldrich Co. All rights reserved.
7
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)
© 2012 Sigma-Aldrich Co. All rights reserved.
8
SLB-IL60Phase Structure
sigma-aldrich.com/il-gc
1,12-Di(tripropylphosphonium)dodecane bis(trifluoromethylsulfonyl)imide
© 2012 Sigma-Aldrich Co. All rights reserved.
9
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
© 2012 Sigma-Aldrich Co. All rights reserved.
10
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
© 2012 Sigma-Aldrich Co. All rights reserved.
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)
© 2012 Sigma-Aldrich Co. All rights reserved.
Reformulated Gasoline with D3606 Oxygenates
50 ºC (6 min) to 265 ºC (10 min) at 15 ºC/min.
12
0 10 20
Time (min)
0
200
400
600
800
1000
1200
1400
1600
1800
1
23
47
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
© 2012 Sigma-Aldrich Co. All rights reserved.
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
sigma-aldrich.com/gc 13
PAHs on a Traditional 5% Silphenylene Phase
© 2012 Sigma-Aldrich Co. All rights reserved.
PAHs on SLB-ILPAH, 20 m x 0.18 mm I.D., 0.05 µm df)
sigma-aldrich.com/gc 14
© 2012 Sigma-Aldrich Co. All rights reserved.
Selected Isomers
sigma-aldrich.com/gc 15
© 2012 Sigma-Aldrich Co. All rights reserved.
Ionic Liquid Water Separations
16
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
© 2012 Sigma-Aldrich Co. All rights reserved.
17
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
18
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
© 2012 Sigma-Aldrich Co. All rights reserved.
SLB-IL 107 SPME Fiber Test STD
19
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
© 2012 Sigma-Aldrich Co. All rights reserved.
C1-C6 Alcohol Mix
20
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.
1
© 2012 Sigma-Aldrich Co. All rights reserved.
Grappa Bassano
21
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
© 2012 Sigma-Aldrich Co. All rights reserved.
Grappino
22
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
23
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
© 2012 Sigma-Aldrich Co. All rights reserved.
Ouzo
24
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.
© 2012 Sigma-Aldrich Co. All rights reserved.
Over-coated PDMS/ DVB SPME Fibers
25
© 2012 Sigma-Aldrich Co. All rights reserved.
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
26
© 2012 Sigma-Aldrich Co. All rights reserved.
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
27
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
28
ERROR: undefined
OFFENDING COMMAND: f‘~
STACK:
