Analysis of Natural Oils and Extracts Using the Low ... · System diagram: LTM ll/Deans/FID-MSD...

Analysis of Natural Oils and Extracts Using the Low Thermal Mass LTM Series II System

June 28, 2011 LTM Series II/ Deans Switch/5975C

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Agilent Technologies Chemical Analysis Group Wilmington, DE USA

Application Outline

Ø Combine a single 5 inch LTM II column with a Deans switch and MSD for the analysis of the enantiomers of Linalool and other terpenoids

Ø Use of independent temperature programming in an second aux oven is demonstrated. This is one of the key advantages of LTM technology installed on the 7890A platform.

Ø The Deans switch is used to heart-cut linalool to a cyclodex column to achieve enantiomer separation.

Ø  Use of LTM technology allows the cyclodex column to be programmed to lower temperatures, prolonging life with lower stationary phase bleed. The cyclodextrin is also protected from higher boiling compound contamination that would lead to poor performance.

Ø  The 5975C is used for detection and confirmation.

June 28, 2011 2 LTM Series II/ Deans Switch/5975C

Relevance

•  Linalool (3,7-dimethyl-1,6-octadien-3-ol) is an important compound in the perfume, food, and alternative medicine industries.

•  With an asymmetric carbon atom, it exists in two forms:

3(R) – flowery fresh scent

3(S)+ woody less fresh scent

•  In natural products, one enantiomer will usually predominate

•  In synthetics, a racemic mixture is found

•  Other important terpenoids can also be separated using the LTM/Deans approach (i.e. citronellol)


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Determining authenticity or adulteration

•  The ratio of linalool enantiomers can be an indication of the compounds origin.

•  If a racemic mixiture is found, linalool is likely of synthetic origin.


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Sample preparation and typical method parameters

Samples: natural oils and extracts diluted in methylene chloride

Method Parameters

Inlet: Split, 280 C

Split ratio: 200:1 to 400:1

Primary column: 30 m x 0.25 mm x 0.25 um DB5ms

LTM column: 30 m x 0.25 mm x 0.25 um CycloDex, constant flow @ 2.5 ml/min

7890 Oven: 70 C (1 min) to 280 C @ 10 C/min, constant flow @ 1.3 ml/min

LTM II: 75 C (7 min) to 130 C @ 2 C/min

5975C: scan 25 to 160 amu

June 28, 2011

LTM Series II/ Deans Switch/5975C 5

LTM Series II

•  Full integration and control by the Agilent 7890A System including 7890 keyboard configuration and parameter display

•  Complete integration in Agilent Chemstation Platforms

•  Constant flow mode of operation

•  Real time display of temperatures/pressures/flows


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LTM Series II

•  System part # : G6680A, 5 inch format with 2 power supplies

•  7890A firmware requirement: A.01.12.1 or greater

•  GC Chemstation: B.04.03 DSP1, includes LTM II control software

•  MSD Chemstation: E.02.02


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LTM Series II IN Segment Out Segment Segment 2

GC Oven GC Oven MSD

Column Segment

Configuring an LTM II Module in Chemstation


System diagram: LTM ll/Deans/FID-MSD

Primary column 30 m x 0.24 mm x 0.25 um DB5ms

2 1

3 NO

NC

Split Inlet 5975C

MSD

LTM II

FID restrictor

PCM

Deans Switch

0.7 m x 0.100 mm

30 m x 0.25 mm x 0.25 um Cyclodex


System diagram: LTM ll/Deans/FID-FID

Primary column

2 1

3 NO

NC

Split Inlet

LTM II

FID restrictor

PCM

Deans Switch

0.5 m x 0.100 mm

FID

20 m x 0.25 mm x 0.25 um Cyclodex


Deans switch setup: MSD configuration


Deans Switch Calculator Primary column: 1.3 ml/min, Cyclodex: 2.5 ml/min


2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 26.00 28.00 0 100000 200000 300000 400000 500000 600000 700000 800000 900000

1000000 1100000 1200000 1300000 1400000 1500000 1600000 1700000 1800000 1900000 2000000 2100000 2200000 2300000 2400000 2500000 2600000

Geranium extract : FID monitor, no cut

7.00 7.50 8.00 8.50 9.00 9.50 10.00 10.50 0 50000

100000 150000 200000 250000 300000 350000 400000 450000 500000

Linalool

Other compounds may coelute with Linalool om primary DB5ms


18.0018.5019.0019.5020.0020.5021.0021.5022.0022.5023.0023.5024.0024.50

20000

40000

60000

80000

100000

120000

140000

160000

Time-->

Abundance

TIC: 00301003.D\data.ms

Geranium extract


Geranium: 3 cuts, 500 to 1 split

Geranium, cuts at: 8.25 to 8.38 (linalool), 9.3 to 9.5 (Methone), 10.0 to 10.9 ( citronellyl formate, B-citronellol, nerol)

1

2

3

4

5

6


5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00

Balm oil

5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00

20.00 20.50 21.00 21.50 22.00 22.50 23.00 23.50

Cut 8.25 min to 8.38 min Linalool

TIC

FID


Cypress oil

Terpinolene

Linalool

14.00 15.00 16.00 17.00 18.00 19.00 20.00 21.00 22.00 23.00

TIC


Jasmin extract

19.00 19.50 20.00 20.50 21.00 21.50 22.00 22.50 23.00 23.50 24.00 24.50

TIC


Lime oil

Linalool

Terpinolene

5.00 10.00 15.00 20.00 25.00 30.00

TIC


Detergent perfume additive

Methyl ester Benzoic acid

Linalool

Tetrahydro linalool

2,6 dimethyl-2-octanol

15.00 16.00 17.00 18.00 19.00 20.00 21.00 22.00 23.00 24.00 25.00 26.00

TIC

A number of compounds are transferred with just the one cut for linalool


Geranium, cuts at: 8.25 to 8.38 (linalool), 9.3 to 9.5 (Methone), 10.0 to 10.9 ( citronellyl formate, B-citronellol, trans-geranoil)

18.00 20.00 22.00 24.00 26.00 28.00 30.00 32.00 34.00 36.00

50000

100000

150000

200000

250000

300000

350000

400000

450000

min

linalool

methone Citronellyl formate

R (-) -B - citronellol

Nerol

Citral

.


LTM ll/DEANS/FID-FID

FID (monitor)

FID (LTM ll)

Linalool •  LTM ll Module: 20 m x 0.25 mm x 0.25 um Cyclodex

•  Faster analysis with some loss of resolution


Summary

LTM series II incorporates a number of new features including full control integrated in Chemstation, and operation in true constant flow mode that assists the analyst with development of new methods. This is especially true with more complex configurations involving the Deans switch and 5975C MSD.

The use of two independent ovens gives the analyst flexibility to optimize analysis of natural oils or synthetic formulations especially where chiral separations can be used for origin and authenticity.

In many applications, analysis time will also be shorter since only compounds of interest are cut to the chiral column.


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Summary

The combination of LTM, CFT Deans switch, and 5975C forms a core system for the solution of a variety of analytical problems beyond the chiral applications shown in this work.

Only a change in column sets as appropriate for the application is required.

Application Note “Analysis of Natural Oils and Extracts Using the Low Thermal Mass LTM Series II System”, Roger L. Firor, Application Note 5990-8151EN

See www.agilent.com/chem


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