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Method of resolving defined known or suspected allergens in a complex mixture of perfume ingredients, and compositions

11002716 · 2021-05-11

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Abstract

Analytical methods that can be employed to reliably separate known or suspected allergens in a complex mixture of fragrance ingredients are described.

Claims

1. A method of resolving defined known or suspected allergens in a complex mixture of perfume ingredients the method comprising the step of: using two-dimensional gas chromatography, resolving defined known or suspected allergens in the complex mixture wherein, the combination of first and second stationary phases is selected on the basis of a clustering analysis of defined known or suspected allergens providing a Separation Efficiency parameter (SE.sub.2D) of 94% or greater wherein SE 2 ⁢ D = 100 n + m × ( n + .Math. i = 1 m ⁢ ( .Math. j = 1 o ⁢ ⁢ Rs 2 ⁢ D , ij ) ) and wherein Rs.sub.2D is the two-dimensional resolution between two neighbouring peaks (a) and (b), corresponding to two different defined known or suspected allergens on a 2D-GC contour plot, given by the formula: Rs 2 ⁢ D = ( 2 × Δ 1 ⁢ tr 2 × ( M r + 1 ) × P M ) 2 + ( 2 × Δ 2 ⁢ tr 2.55 × ( FWHH a 2 + FWHH b 2 ) ) 2 and wherein M.sub.r is the average number of time each peak is sampled by the modulator, rounded to the upper value, P.sub.M is the 2D-GC modulation period in seconds, Δ.sup.1tr is the difference of retention times between two neighbouring peaks (a) and (b) on the first dimension (x-axis); Δ.sup.2tr is the difference of retention times between the same two neighbouring peaks (a) and (b) on the second dimension (y-axis);.sup.2FWHH.sub.a is the second dimension peak width of a peak (a) at half height and .sup.2FWHH.sub.b is the second dimension peak width of a peak (b) at half height; two defined known or suspected allergens having an Rs.sub.2D value of 1 or higher are well separated and are referred to as Singletons (S); and two defined known or suspected allergens having an Rs.sub.2D value of less than 1 are a cluster; and wherein n is the number of Singletons (S); m is the number of defined known or suspected allergens belonging to a cluster; o is the number of clusters for a given known or suspected allergens; and Rs.sub.2D,ijis the Rs2D value for a defined analytical target i in a given cluster j.

2. The method of claim 1 wherein the first stationary phase has an intermediate polarity, and the second stationary phase is relatively polar compared with the first stationary phase.

3. The method of claim 2 wherein the first stationary phase is an arylene-modified diphenyl-dimethyl siloxane copolymer stationary phase.

4. The method of claim 3 wherein arylene-modified diphenyl-dimethyl siloxane copolymer comprises 20 to about 60 wt % diphenylsiloxane moieties and about 40 to about 80 wt % arylene dimethyl siloxane moieties, wherein the weight percentage (wt %) is relative to the total weight of the copolymer.

5. The method of claim 4, wherein arylene-modified diphenyl-dimethyl siloxane copolymer comprises 30 to about 40 wt % diphenylsiloxane moieties and about 60 to about 70 wt % arylene dimethyl siloxane moieties, wherein the weight percentage (wt %) is relative to the total weight of the copolymer.

6. The method of claim 5, wherein arylene-modified diphenyl-dimethyl siloxane copolymer comprises 33 to about 38 wt % diphenylsiloxane moieties and about 62 to about 67 wt % arylene dimethyl siloxane moieties, wherein the weight percentage (wt %) is relative to the total weight of the copolymer.

7. The method of claim 3 wherein arylene-modified diphenyl-dimethyl siloxane copolymer is a copolymer comprising about 35% diphenylsiloxane moieties and about 65% dimethylsiloxane and arylene dimethyl siloxane moieties.

8. The method of claim 1, wherein the second stationary phase is a (polyethylene-glycol) wax.

9. The method of claim 1, wherein the known or suspected allergen is selected from the group consisting of: Acetyl Cedrene (main isomer) (32388-55-9); Alpha Isomethylionone (127-51-5); Amyl Cinnamic Alcohol (E) (101-85-9); Amyl Cinnamic Aldehyde (E) (122-40-7); Amyl Salicylate (ISO-) (87-20-7); Amyl Salicylate (N-) (2050-08-0); Anethole Trans (E) (4180-23-8); Anisyl Alcohol (105-13-5); Benzaldehyde (100-52-7); Benzyl Alcohol (100-51-6); Benzyl Benzoate (120-51-4); Benzyl Cinnamate (E) (103-41-3); Benzyl Cyanide (140-29-4); Benzyl Salicylate (118-58-1); Camphor (76-22-2); Carvone (99-49-0); Caryophyllene Beta (87-44-5); Cinnamic Alcohol (E) (104-54-1); Cinnamic Aldehyde (E) (104-55-2); Citronellol (106-22-9); Coumarin (91-64-5); Hydroxyisohexyl 3-cyclohexene carboxaldehyde (Cyclohexal/Lyral major) (31906-04-4); Hydroxyisohexyl 3-cyclohexene carboxaldehyde (Cyclohexal/Lyral minor) (51414-25-6); Damascenone Beta (23696-85-7); Damascone Alpha (E) (24720-09-0); Damascone Alpha (Z) (23726-94-5); Damascone Beta (E) (23726-91-2); Damascone Beta (Z) (23726-92-3); Damascone Delta cis/trans (71048-83-4); Damascone Delta trans/cis (n/a); Damascone Delta trans/trans (71048-82-3); Di Iso-Butyl Phthalate (84-69-5); Di isopentyl phthalate (605-50-5); Di Isopropyl Phthalate (605-45-8); Di n-Butyl Phthalate (84-74-2); Di n-pentyl phthalate (131-18-0); Dicyclohexyl phthalate (84-61-7); Diethyl Hexyl Phthalate (117-81-7); Diethyl Phthalate (84-66-2); Dimethyl Phthalate (131-11-3); Dimethyl Benzyl Carbinyl Acetate (151-05-3); Ebanol 1 (67801-20-1); Ebanol 2 (67801-20-1); Estragol (140-67-0); Eugenol (97-53-0); Eugenyl acetate (93-28-7); Farnesol (E)(E) (106-28-5); Farnesol (Z)(E) (3790-71-4); Farnesol (E)(Z) (3879-60-5); Farnesol (Z)(Z) (16106-95-9); Galaxolide (Cis) (252933-49-6); Galaxolide (Trans) (252933-48-5); Geranial (141-27-5); Geraniol (106-24-1); Geranyl Acetate (105-87-3); Hexadecanolide (109-29-5); Hexyl Cinnamic Aldehyde (E) (101-86-0); Hydroxycitronellal (107-75-5); Iso E Super Alpha (68155-66-8); Iso E Super Beta (54464-57-2); Iso E Super Gamma (68155-67-9); Iso E Super minor (54464-59-4); Isoeugenol (E) (5932-68-3); Isoeugenol (Z) (5912-86-7); Isoeugenyl Acetate (93-29-8); Lilial (80-54-6); Limonene (5989-27-5); Linalool (78-70-6); Linalyl Acetate (115-95-7); Majantol (103694-68-4); Menthol (1490-04-6); Methoxycoumarin-7 (531-59-9); Methyl Eugenol (93-15-2); Methyl Heptine Carbonate (111-12-6); Methyl Octine Carbonate (111-80-8); Methyl Salicylate (119-36-8); Neral (106-26-3); n-pentyl isopentyl phthalate (84777-06-0); Phenyl Acetaldehyde (122-78-1); Pinene Alpha (80-56-8); Pinene Beta (127-91-3); Propylidene Phthalide 3- (E) (56014-72-3); Propylidene Phthalide 3- (Z) (94704-89-9); Salicylaldehyde (90-02-8); Santalol Alpha (115-71-9); Santalol Beta (77-42-9); Sclareol (515-03-7); Terpinene Alpha (99-86-5); Terpineol Alpha (98-55-5); Terpineol Beta cis (7299-41-4); Terpineol Beta trans (7299-40-3); Terpineol Delta (7299-42-5); Terpineol Gamma (586-81-2); Terpinolene (586-62-9); and Vanillin (121-33-5).

10. The method of claim 1, wherein the complex mixture of perfume ingredients comprises at least one known or suspected allergen selected from the group consisting of: Acetyl Cedrene (main isomer) (32388-55-9); Alpha Isomethylionone (127-51-5); Amyl Cinnamic Alcohol (E) (101-85-9); Amyl Cinnamic Aldehyde (E) (122-40-7); Amyl Salicylate (ISO-) (87-20-7); Amyl Salicylate (N-) (2050-08-0); Anethole Trans (E) (4180-23-8); Anisyl Alcohol (105-13-5); Benzaldehyde (100-52-7); Benzyl Alcohol (100-51-6); Benzyl Benzoate (120-51-4); Benzyl Cinnamate (E) (103-41-3); Benzyl Cyanide (140-29-4); Benzyl Salicylate (118-58-1); Camphor (76-22-2); Carvone (99-49-0); Caryophyllene Beta (87-44-5); Cinnamic Alcohol (E) (104-54-1); Cinnamic Aldehyde (E) (104-55-2); Citronellol (106-22-9); Coumarin (91-64-5); Hydroxyisohexyl 3-cyclohexene carboxaldehyde (Cyclohexal/Lyral major) (31906-04-4); Hydroxyisohexyl 3-cyclohexene carboxaldehyde (Cyclohexal/Lyral minor) (51414-25-6); Damascenone Beta (23696-85-7); Damascone Alpha (E) (24720-09-0); Damascone Alpha (Z) (23726-94-5); Damascone Beta (E) (23726-91-2); Damascone Beta (Z) (23726-92-3); Damascone Delta cis/trans (71048-83-4); Damascone Delta trans/cis (n/a); Damascone Delta trans/trans (71048-82-3); Di Iso-Butyl Phthalate (84-69-5); Di isopentyl phthalate (605-50-5); Di Isopropyl Phthalate (605-45-8); Di n-Butyl Phthalate (84-74-2); Di n-pentyl phthalate (131-18-0); Dicyclohexyl phthalate (84-61-7); Diethyl Hexyl Phthalate (117-81-7); Diethyl Phthalate (84-66-2); Dimethyl Phthalate (131-11-3); Dimethyl Benzyl Carbinyl Acetate (151-05-3); Ebanol 1 (67801-20-1); Ebanol 2 (67801-20-1); Estragol (140-67-0); Eugenol (97-53-0); Eugenyl acetate (93-28-7); Farnesol (E)(E) (106-28-5); Farnesol (Z)(E) (3790-71-4); Farnesol (E)(Z) (3879-60-5); Farnesol (Z)(Z) (16106-95-9); Galaxolide (Cis) (252933-49-6); Galaxolide (Trans) (252933-48-5); Geranial (141-27-5); Geraniol (106-24-1); Geranyl Acetate (105-87-3); Hexadecanolide (109-29-5); Hexyl Cinnamic Aldehyde (E) (101-86-0); Hydroxycitronellal (107-75-5); Iso E Super Alpha (68155-66-8); Iso E Super Beta (54464-57-2); Iso E Super Gamma (68155-67-9); Iso E Super minor (54464-59-4); Isoeugenol (E) (5932-68-3); Isoeugenol (Z) (5912-86-7); Isoeugenyl Acetate (93-29-8); Lilial (80-54-6); Limonene (5989-27-5); Linalool (78-70-6); Linalyl Acetate (115-95-7); Majantol (103694-68-4); Menthol (1490-04-6); Methoxycoumarin-7 (531-59-9); Methyl Eugenol (93-15-2); Methyl Heptine Carbonate (111-12-6); Methyl Octine Carbonate (111-80-8); Methyl Salicylate (119-36-8); Neral (106-26-3); n-pentyl isopentyl phthalate (84777-06-0); Phenyl Acetaldehyde (122-78-1); Pinene Alpha (80-56-8); Pinene Beta (127-91-3); Propylidene Phthalide 3- (E) (56014-72-3); Propylidene Phthalide 3- (Z) (94704-89-9); Salicylaldehyde (90-02-8); Santalol Alpha (115-71-9); Santalol Beta (77-42-9); Sclareol (515-03-7); Terpinene Alpha (99-86-5); Terpineol Alpha (98-55-5); Terpineol Beta cis (7299-41-4); Terpineol Beta trans (7299-40-3); Terpineol Delta (7299-42-5); Terpineol Gamma (586-81-2); Terpinolene (586-62-9); and Vanillin (121-33-5).

11. A method of preparing a perfume composition, the method comprising the step of including in said composition at least one perfume ingredient that is either not a defined known or suspected allergen, or is an ingredient that is substantially free of defined known or suspected allergens, as determined by two-dimensional gas chromatography, wherein the combination of stationary phases for two-dimensional comprehensive gas chromatography are selected on the basis of the method of claim 1.

Description

FIGURES

(1) FIG. 1: Representation of neighbouring peaks on a 2D GC plot;

(2) FIG. 2: Separation of Damascenone Beta and Damascone Alpha (VF35×Wax; Rs.sub.2D=0.74). These two analytical targets are clustered, according to this invention.

(3) FIG. 3: Separation of Geranyl Acetate and Damascone Delta trans/trans (Rtx-5Sil×Wax; Rs.sub.2D=0.93). These two analytical targets are clustered, according to this invention.

(4) FIG. 4: Separation of Cyclohexal/Lyral minor and Cyclohexal/Lyral major (VF35×Wax; Rs.sub.2D=1.23). These two analytical targets are Singletons, according to this invention.

(5) FIG. 5: Separation of Carvone and Geranial (VF35×Wax; Rs.sub.2D=1.35). These two analytical targets are Singletons, according to this invention.

EXAMPLES

Example 1: Two-Dimensional Gas Chromatographic Procedure

(6) The 95 ingredients reported in Table 1 (see description herein above) were dissolved in METHYL TERT-BUTYL ETHER at a level of 250 ppm (0.0250% by weight) each. In cases an ingredient was a mixture of isomers, the amount was adapted in such a way that the most abundant isomer was at a level of 250 ppm in the solution.

(7) All GC×GC experiments were carried out using with a Pegasus 4D GC×GC-TOFMS from LECO (St. Joseph, Mich., USA), consisting of a 7890B GC from (Agilent Technologies, USA), a LN2 cooled thermal modulator from LECO and a Pegasus HT TOFMS from LECO. The MS part was operated in an EI mode at −70 eV, with an acquisition frequency set at 150 Hz in a mass ranging from 35 to 350 g/mol and with a multiple-plate voltage set at −1450 V. The GC transfer line was set at 245° C. and consisted of the secondary column. ChromaTOF (LECO) was used for controlling the 2D-GC set-up, for data acquisition and for data processing. Injections of the mixture of defined analytical targets were performed with a split injector with an injection temperature at 250° C., a split ratio at 1:100 and an injection volume of 0.5 μL. Carrier gas (Helium) was delivered at a constant flow (1.3 mL/min). For comparison purpose, the same first column geometry was used for all 2D-GC set-ups investigated (60 m×0.25 mm ID, 0.25 μm film thickness). The reference length of the secondary column was set at 1 m (150 mm ID, 0.15 μm film thickness) and was possibly extended to 2 m in case of available 2D space with reference comparison parameters. Connections between the primary and the two secondary columns were done by a SilTite® μ-Union (SGE Ringwood, Victoria, Australia). The reference 2D modulation period was set at 5 s with a hot pulse at 1.2 s (+15° C. versus the secondary column) and 2D modulation period was possibly extended to 7 s in case of wrap-around in secondary dimension with the reference comparison parameters.

(8) A GC program-temperature ramp was implemented from 50° C. (1 min) to 245° C. when the 2D-GC set-up contains a Wax column and 300° C. when not (for several minutes depending of each 2D-GC set-up) at 2° C./min (see Table 2). A reference temperature offset for the secondary column was set at +15° C. versus the main oven and was possibly extended to +25° C. m in case of wrap-around in secondary dimension with reference comparison parameters. Secondary dimension retention times were corrected with an offset from −0.5 s to −1.0 s in order to maximize the available 2D space. The exact set of parameters for each combination of stationary phases are reported in Table 2.

(9) TABLE-US-00002 TABLE 2 Specific operating conditions for each 2D-GC set-up Lenght of the secondary Final temperature of ID 2D-GC set-ups Modulation period (s) column (m) the main oven (° C.) 1 Rtx-5Sil × Wax 7 1 245 2 Rtx-5Sil × Rtx-17Sil 5 2 300 3 Wax × Rtx-5Sil 5 2 245 4 VF35 × Wax 5 1 245 5 Rtx-17Sil × Wax 5 1 245 Duration time at final Temperature offset of Second dimension ID 2D-GC set-ups temperature (° C.) the secondary oven (° C.) time offset (s) 1 Rtx-5Sil × Wax 20 +25 −0.5 2 Rtx-5Sil × Rtx-17Sil 10 +15 −1 3 Wax × Rtx-5Sil 35 +15 −1 4 VF35 × Wax 30 +20 −0.5 5 Rtx-17Sil × Wax 35 +15 −0.5

Examples 2 to 6: Separation of Defined Analytical Targets

(10) The result of the two-dimensional gas chromatographic separation of the 95 allergens are reported in Tables 3 to 7 are the experimental data, including retention times in both first (.sup.1tr) and second (.sup.2tr) dimensions, width of the peak at half height in the second dimension (.sup.2width), and the resolution between neighboring peaks (Rs.sub.2D, from the first closest neighbouring peak to the fifth closest neighbouring peak).

(11) Legend of Tables 3 to 7:

(12) .sup.1tr=First Dimension Time (s) .sup.2tr=Second Dimension Time (s) .sup.2Width=Full Width at Half Height on secondary dimension Rs.sub.2D 1=Rs.sub.2D with the first neighbour Rs.sub.2D 2=Rs.sub.2D with the second neighbour Rs.sub.2D 3=Rs.sub.2D with the third neighbour Rs.sub.2D 4=Rs.sub.2D with the fourth neighbor Rs.sub.2D 5=Rs.sub.2D with the fifth neighbour TC SE.sub.2D=Total contribution to SE2D. This total contribution is the sum of the Rs.sub.2D for the corresponding target.

(13) Table 8 shows an example of how the ingredients are clustered, based on their Rs.sub.2D and SE.sub.2D values. The stationary phase combination was the same as in Table 3. The targets having neighbours with Rs.sub.2D larger than 1 are singleton and therefore not reported in Table 7. As apparent from the table, TERPINEOL BETA TRANS and TERPINEOL DELTA have, for example, a mutual of 0.78, which is smaller than 1, and therefore belong to the same cluster C1. TERPINEOL DELTA has an additional neighbour peak width a of 1.58, which is larger than 1 and therefore means that this peak is sufficiently apart from TERPINEOL DELTA not to be in a cluster with the latter. (Note that Table 2 shows that this third target is MENTHOL).

(14) Table 9 shows a comprehensive list of clustered targets, meaning all peaks having at least one neighbouring peak with Rs.sub.2D smaller than 1.

(15) Table 10 summarizes all results from Tables 3 to 7 with the values of and parameters in Equations 1, 2, 5, 6 and 7.

(16) TABLE-US-00003 TABLE 3 Experimental data for Rtx5 × Wax stationary phase combination (Example 2) List of targets .sup.1tr .sup.2tr .sup.2Width Rs.sub.2D 1 Rs.sub.2D 2 Rs.sub.2D 2 Rs.sub.2D 4 Rs.sub.2D 5 TC SE.sub.2D Acetyl Cedrene (main isomer) 4235 0.633 0.036966 7.155109 1 Alpha Isomethylionone 3227 0.514 0.035604 1 Amyl Cinnamic Alcohol (E) 3955 1.656 0.070874 4.178726 5.075817 5.137754 1 Amyl Cinnamic Aldehyde (E) 3829 0.923 0.047709 1.364748 1 Amyl Salicylate (ISO-) 3444 0.738 0.038064 1.047318 1 Amyl Salicylate (N-) 3584 0.777 0.039837 7.515063 1 Anethole Trans (E) 2499 0.963 0.053992 2.972017 12.76782 1 Anisyl Alcohol 2478 4.837 0.18442 10.88749 12.76782 1 Benzaldehyde 1148 1.359 0.070947 1 Benzyl Alcohol 1435 4.467 0.17169 16.15586 1 Benzyl Benzoate 4228 1.623 0.071624 7.155109 1 Benzyl Cinnamate (E) 5187 2.104 0.083973 6.511547 1 Benzyl Cyanide 1869 2.943 0.12699 1 Benzyl Salicylate 4543 1.728 0.071789 1 Camphor 1925 0.586 0.044176 2.23663 1 Carvone 2331 0.85 0.04671 2.379768 4.297913 1 Caryophyllene Beta 3038 0.303 0.031179 1 Cinnamic Alcohol (E) 2576 4.302 0.16619 1 Cinnamic Aldehyde (E) 2443 2.19 0.097562 8.205283 1 Citronellol 2247 0.949 0.047874 1 Coumarin 3087 3.702 0.15304 12.86211 1 Damascenone Beta 2870 0.646 0.041526 0.900152 1.289077 1.494049 1.632791 0.9001524 Damascone Alpha (E) 2912 0.567 0.039962 0.843133 1.200603 4.354721 16.06587 0.84313277 Damascone Alpha (Z) 2772 0.494 0.032495 11.03334 1 Damascone Beta (E) 2982 0.58 0.037195 6.781579 11.11522 1 Damascone Beta (Z) 2884 0.507 0.036201 1.036743 1.039212 1.200603 1.494049 1 Damascone Delta cis/trans 2891 0.6 0.036428 0.843133 0.900152 1.036743 0.75894799 Damascone Delta trans/cis 2688 0.487 0.033275 1 Damascone Delta trans/trans 2842 0.567 0.03833 0.93155 1.289077 0.9315502 Di Iso-Butyl Phthalate 4501 0.969 0.048177 1 Di isopentyl phthalate 5082 0.956 0.047532 1 Di Isopropyl Phthalate 3836 1.095 0.052944 1.364748 3.041261 5.054776 1 Di n-Butyl Phthalate 4781 1.068 0.050811 1 Di n-pentyl phthalate 5306 1.048 0.050069 1 Dicyclohexyl phthalate 6195 3.279 0.13412 1 Diethyl Hexyl Phthalate 6251 1.781 0.081122 1 Diethyl Phthalate 3626 1.517 0.068273 1 Dimethyl Benzyl Carbinyl 2618 0.692 0.050032 1 Acetate Dimethyl Phthalate 3122 2.19 0.091771 1.526838 9.391394 9.738884 1 Ebanol 1 3108 0.6 0.036457 1.108452 9.738884 10.95377 12.86211 1 Ebanol 2 3136 0.639 0.037954 1.108452 9.391394 10.62555 1 Estragol 2135 0.81 0.0464 0.515836 0.542744 0.788273 3.333814 0.22069028 Eugenol 2758 2.223 0.090546 11.03334 1 Eugenyl acetate 3367 1.438 0.064632 1 Farnesol (E)(E) 4053 0.89 0.045083 1.892172 12.56978 1 Farnesol (E)(Z) 3983 0.86 0.053156 0 2.381348 5.075817 0 Farnesol (Z)(E) 3983 0.86 0.053156 0 2.295438 5.137754 0 Farnesol (Z)(Z) 3892 0.85 0.041714 3.008755 3.086871 3.306978 4.862365 5.076328 1 Galaxolide (Cis) 4459 0.613 0.039151 0.264398 0.26439839 Galaxolide (Trans) 4466 0.619 0.038465 0.264398 0.26439839 Geranial 2422 0.738 0.041848 8.205283 1 Geraniol 2345 1.154 0.05591 2.379768 6.469175 1 Geranyl Acetate 2856 0.494 0.03541 0.93155 1.039212 1.632791 0.9315502 Hexadecanolide 4725 0.593 0.036262 1 Hexyl Cinnamic Aldehyde (E) 4151 0.89 0.045452 1 Hydroxycitronellal 2492 1.405 0.063091 2.972017 10.88749 1 Hydroxyisohexyl 3-cyclohexene 3892 1.53 0.067972 1.030023 4.862365 7.402963 7.452571 7.637425 1 carboxaldehyde (Cyclohexal/Lyral major) Hydroxyisohexyl 3-cyclohexene 3864 1.524 0.064631 1.030023 3.041261 5.076328 7.6884 7.776542 1 carboxaldehyde (Cyclohexal/Lyral minor) Iso E Super Alpha 3997 0.606 0.035899 2.295438 2.381348 1 Iso E Super Beta 3885 0.547 0.035541 0.772059 1.053415 3.086871 7.452571 7.6884 0.77205882 Iso E Super Gamma 3913 0.567 0.034613 1.053415 3.008755 4.277514 7.402963 1 Iso E Super minor 3864 0.547 0.033905 0.772059 3.306978 5.054776 7.637425 7.776542 0.77205882 Isoeugenol (E) 3122 2.573 0.10497 1.526838 10.62555 10.95377 1 Isoeugenol (Z) 2961 2.349 0.087931 7.175595 11.11522 1 Isoeugenyl Acetate 3689 1.642 0.072461 1 Lilial 3416 0.758 0.043279 1.047318 1 Limonene 1421 0.256 0.032844 16.15586 1 Linalool 1715 0.718 0.042539 1 Linalyl Acetate 2345 0.408 0.034534 4.297913 6.469175 1 Majantol 2996 1.477 0.066846 6.781579 1 Menthol 2051 0.758 0.045037 1.581179 1 Methoxycoumarin-7 4081 4.236 0.1644 11.3582 12.56978 1 Methyl Eugenol 2940 1.068 0.052903 4.354721 7.175595 14.11996 1 Methyl Heptine Carbonate 2135 0.72 0.043148 0.788273 1.108792 1.261058 4.13508 0.78827261 Methyl Octine Carbonate 2541 0.679 0.041633 1 Methyl Salicylate 2114 1.233 0.055896 2.823862 3.333814 4.13508 1 Neral 2296 0.712 0.039618 1 n-pentyl isopentyl phthalate 5194 1.002 0.048866 6.511547 1 Phenyl Acetaldehyde 1477 1.491 0.066865 1.510067 1 Pinene Alpha 1043 0.164 0.033474 1 Pinene Beta 1218 0.21 0.038099 1 Propylidene Phthalide 3-(E) 3570 1.979 0.085905 7.515063 1 Propylidene Phthalide 3-(Z) 3731 2.263 0.093138 1 Salicylaldehyde 1484 1.761 0.075452 1.510067 1 Santalol Alpha 3934 1.022 0.050207 4.178726 4.277514 1 Santalol Beta 4067 1.114 0.051404 1.892172 11.3582 1 Sclareol 5516 1.689 0.072529 1 Terpinene Alpha 1372 0.243 0.030979 1 Terpineol Alpha 2128 0.864 0.048338 0.515836 0.823545 1.261058 2.823862 0.42481459 Terpineol Beta cis 1932 0.831 0.042312 2.23663 1 Terpineol Beta trans 2009 0.956 0.046408 0.783489 0.78348909 Terpineol Delta 2023 0.89 0.041224 0.783489 1.581179 0.78348909 Terpineol Gamma 2149 0.83 0.0447 0.542744 0.823545 1.108792 0.44697387 Terpinolene 1659 0.289 0.029896 1 Vanillin 2926 6.619 0.25564 14.11996 16.06587 1

(17) TABLE-US-00004 TABLE 4 Experimental data for Rtx5 × Rx17 stationary phase combination (Example 3) TC List of targets .sup.1tr .sup.2tr .sup.2Width Rs.sub.2D 1 Rs.sub.2D 2 Rs.sub.2D 2 Rs.sub.2D 4 Rs.sub.2D 5 SE.sub.2D Acetyl Cedrene (main isomer) 4290 2.085 0.078985 4.21 1.00 Alpha Isomethylionone 3280 1.655 0.070744 1.00 Amyl Cinnamic Alcohol (E) 4005 2.2 0.07523 2.11 3.33 3.40 1.00 Amyl Cinnamic Aldehyde (E) 3880 2.19 0.076798 1.09 1.00 Amyl Salicylate (ISO-) 3495 1.85 0.066083 1.68 1.00 Amyl Salicylate (N-) 3640 1.89 0.064649 5.29 1.00 Anethole Trans (E) 2555 2.07 0.067802 1.68 3.55 1.00 Anisyl Alcohol 2535 2.735 0.084998 3.55 4.79 1.00 Benzaldehyde 1190 1.96 0.083965 1.00 Benzyl Alcohol 1480 2.11 0.079133 5.01 1.00 Benzyl Benzoate 4280 3.005 0.093454 4.21 1.00 Benzyl Cinnamate (E) 5245 3.33 0.1021 3.87 1.00 Benzyl Cyanide 1925 2.84 0.089987 1.00 Benzyl Salicylate 4600 2.965 0.089558 1.00 Camphor 1980 1.845 0.10754 1.66 1.00 Carvone 2380 2.035 0.075333 2.14 2.97 4.15 1.00 Caryophyllene Beta 3095 1.415 0.067419 1.00 Cinnamic Alcohol (E) 2630 2.595 0.082422 1.00 Cinnamic Aldehyde (E) 2495 2.74 0.083831 5.26 1.00 Citronellol 2300 1.375 0.061069 1.00 Coumarin 3140 3.785 0.11183 10.56 1.00 Damascenone Beta 2925 1.885 0.07937 1.03 1.03 1.50 2.15 1.00 Damascone Alpha (E) 2965 1.795 0.07685 0.99 1.23 2.88 6.48 0.99 Damascone Alpha (Z) 2825 1.715 0.078681 2.59 1.00 Damascone Beta (E) 3040 1.835 0.078473 1.00 2.86 1.00 Damascone Beta (Z) 2940 1.777 0.038692 0.37 1.03 1.23 2.48 0.37 Damascone Delta cis/trans 2945 1.82 0.08277 0.37 0.99 1.03 6.31 0.37 Damascone Delta trans/cis 2740 1.655 0.077153 1.00 Damascone Delta trans/trans 2900 1.715 0.075344 1.20 1.50 1.00 Di Iso-Butyl Phthalate 4555 2.36 0.082806 1.00 Di isopentyl phthalate 5140 2.36 0.08633 1.00 Di Isopropyl Phthalate 3890 2.39 0.084574 1.09 1.51 2.83 1.00 Di n-Butyl Phthalate 4835 2.51 0.085801 1.00 Di n-pentyl phthalate 5355 2.485 0.082997 1.00 Dicyclohexyl phthalate 6255 3.825 0.11476 1.00 Diethyl Hexyl Phthalate 6300 2.37 0.081362 1.00 Diethyl Phthalate 3675 2.745 0.090351 1.00 Dimethyl Benzyl Carbinyl 2670 1.83 0.075734 1.00 Acetate Dimethyl Phthalate 3175 3.02 0.095451 2.92 7.80 7.86 1.00 Ebanol 1 3160 1.43 0.063834 5.37 7.86 10.56 1.00 Ebanol 2 3195 1.435 0.065157 5.26 7.80 1.00 Estragol 2190 1.865 0.06567 0.46 1.61 1.69 1.69 0.46 Eugenol 2815 2.215 0.075385 2.59 1.00 Eugenyl acetate 3420 2.58 0.084525 1.00 Farnesol (E)(E) 4110 1.7 0.062999 1.78 1.00 Farnesol (E)(Z) 4035 1.655 0.064011 0.00 1.73 3.40 0.00 Farnesol (Z)(E) 4035 1.66 0.066779 0.00 1.68 3.33 0.00 Farnesol (Z)(Z) 3970 1.691 0.054276 1.23 1.37 1.67 4.00 1.00 Galaxolide (Cis) 4515 2.22 0.083539 0.26 0.26 Galaxolide (Trans) 4520 2.235 0.082772 0.26 0.26 Geranial 2470 1.755 0.067246 5.26 1.00 Geraniol 2400 1.54 0.063025 1.50 2.97 1.00 Geranyl Acetate 2910 1.525 0.060094 1.20 2.15 2.48 1.00 Hexadecanolide 4785 2.145 0.078587 1.00 Hexyl Cinnamic Aldehyde (E) 4210 2.155 0.075698 1.00 Hydroxycitronellal 2545 1.785 0.071342 1.68 4.79 1.00 Hydroxyisohexyl 3-cyclohexene 3945 2.34 0.079505 1.23 2.32 2.62 2.79 4.00 1.00 carboxaldehyde (Cyclohexal/Lyral major) Hydroxyisohexyl 3-cyclohexene 3920 2.315 0.080616 1.23 1.51 2.24 2.50 1.00 carboxaldehyde (Cyclohexal/Lyral minor) Iso E Super Alpha 4050 1.93 0.07364 1.68 1.73 1.00 Iso E Super Beta 3945 1.88 0.076174 1.23 1.47 1.67 2.32 2.50 1.00 Iso E Super Gamma 3970 1.89 0.07261 1.02 1.23 1.23 2.62 1.00 Iso E Super minor 3915 1.89 0.069418 1.47 2.24 2.79 2.83 1.00 Isoeugenol (E) 3180 2.38 0.077226 2.92 5.26 5.37 1.00 Isoeugenol (Z) 3015 2.333 0.072664 1.01 2.86 1.00 Isoeugenyl Acetate 3740 2.69 0.08576 1.00 Lilial 3470 2.055 0.074164 1.68 1.00 Limonene 1475 1.055 0.08622 5.01 1.00 Linalool 1765 1.225 0.073398 1.00 Linalyl Acetate 2395 1.295 0.066895 1.50 4.15 1.00 Majantol 3050 2.005 0.07398 1.00 1.00 Menthol 2105 1.4 0.069163 1.77 1.00 Methoxycoumarin-7 4145 4.14 0.12153 8.68 1.00 Methyl Eugenol 2995 2.285 0.078575 1.01 2.88 4.32 1.00 Methyl Heptine Carbonate 2185 1.8 0.067148 0.46 1.25 1.44 1.79 0.46 Methyl Octine Carbonate 2595 1.77 0.064649 1.00 Methyl Salicylate 2170 2.09 0.072635 1.61 1.79 2.82 3.12 1.00 Neral 2355 1.71 0.069514 2.14 1.00 n-pentyl isopentyl phthalate 5250 2.416 0.083471 3.87 1.00 Phenyl Acetaldehyde 1525 2.22 0.08114 0.71 0.71 Pinene Alpha 1090 0.795 0.092236 1.00 Pinene Beta 1265 0.965 0.098099 1.00 Propylidene Phthalide 3-(E) 3625 2.925 0.090344 5.29 1.00 Propylidene Phthalide 3-(Z) 3785 3.175 0.096111 1.00 Salicylaldehyde 1535 2.115 0.079171 0.71 0.71 Santalol Alpha 3990 1.84 0.067159 1.02 1.37 2.11 1.00 Santalol Beta 4125 1.985 0.07445 1.78 8.68 1.00 Sclareol 5570 2.545 0.083208 1.00 Terpinene Alpha 1420 1.035 0.083167 1.00 Terpineol Alpha 2180 1.585 0.070044 0.98 1.25 1.69 2.82 0.98 Terpineol Beta cis 1985 1.46 0.075841 1.66 1.00 Terpineol Beta trans 2060 1.545 0.076965 0.76 0.76 Terpineol Delta 2075 1.585 0.077601 0.76 1.77 0.76 Terpineol Gamma 2200 1.58 0.07256 0.98 1.44 1.69 3.12 0.98 Terpinolene 1715 1.23 0.07357 1.00 Vanillin 2975 3.225 0.096758 4.32 6.31 6.48 1.00

(18) TABLE-US-00005 TABLE 5 Experimental data for Wax × Rx5 stationary phase combination (Example 4) TC List of targets .sup.1tr .sup.2tr .sup.2Width Rs.sub.2D 1 Rs.sub.2D 2 Rs.sub.2D 2 Rs.sub.2D 4 Rs.sub.2D 5 SE.sub.2D Acetyl Cedrene (main isomer) 4415 2.11 0.065 1.00 Alpha Isomethylionone 3310 2.08 0.064 9.11 1.00 Amyl Cinnamic Alcohol (E) 5185 0.915 0.037 0.76 3.84 0.76 Amyl Cinnamic Aldehyde (E) 4490 1.335 0.047 4.12 6.05 1.00 Amyl Salicylate (ISO-) 3880 1.545 0.050 1.34 5.19 7.74 1.00 Amyl Salicylate (N-) 4075 1.49 0.049 1.00 Anethole Trans (E) 3250 1.12 0.040 4.34 1.00 Anisyl Alcohol 4550 0.54 0.030 0.55 8.23 0.55 Benzaldehyde 2230 0.75 0.036 1.00 Benzyl Alcohol 3400 0.49 0.028 11.16 1.00 Benzyl Benzoate 5405 1.01 0.040 1.00 Benzyl Cinnamate (E) 6865 1.62 0.055 1.00 Benzyl Cyanide 3565 0.595 0.031 1.00 Benzyl Salicylate 5760 1.04 0.039 1.00 Camphor 2190 1.66 0.054 1.00 Carvone 2945 1.245 0.043 0.51 5.93 0.51 Caryophyllene Beta 2480 4.115 0.113 1.00 Cinnamic Alcohol (E) 4560 0.56 0.031 0.55 8.08 0.55 Cinnamic Aldehyde (E) 3895 0.73 0.033 7.17 7.74 12.28 1.00 Citronellol 3040 1.005 0.038 3.94 6.39 6.76 1.00 Coumarin 4985 0.665 0.033 3.52 1.00 Damascenone Beta 3220 1.595 0.052 1.56 4.34 1.00 Damascone Alpha (E) 3130 1.795 0.057 0.31 0.31 Damascone Alpha (Z) 2830 2.075 0.064 6.84 6.98 1.00 Damascone Beta (E) 3210 1.8 0.057 1.56 1.00 Damascone Beta (Z) 2975 2.03 0.064 5.17 5.93 1.00 Damascone Delta cis/trans 3135 1.77 0.050 0.31 0.31 Damascone Delta trans/cis 2735 2.1 0.065 6.55 7.20 7.85 1.00 Damascone Delta trans/trans 3050 1.825 0.057 1.54 3.09 6.76 1.00 Di Iso-Butyl Phthalate 5195 1.33 0.048 3.84 4.32 1.00 Di isopentyl phthalate 5700 1.49 0.052 12.72 1.00 Di Isopropyl Phthalate 4685 1.125 0.042 1.72 1.89 7.24 1.00 Di n-Butyl Phthalate 5550 1.295 0.047 1.00 Di n-pentyl phthalate 5980 1.675 0.055 1.00 Dicyclohexyl phthalate 5710 4.415 0.128 12.72 1.00 Diethyl Hexyl Phthalate 6905 4.105 0.126 1.00 Diethyl Phthalate 4775 0.92 0.037 4.78 10.79 1.00 Dimethyl Benzyl Carbinyl 3065 1.42 0.049 3.09 3.94 4.52 1.00 Acetate Dimethyl Phthalate 4595 0.74 0.034 1.00 Ebanol 1 3415 1.67 0.055 11.16 1.00 Ebanol 2 3520 1.56 0.052 1.00 Estragol 2735 1.215 0.041 0.95 2.01 6.55 0.95 Eugenol 4250 0.715 0.032 1.00 Eugenyl acetate 4490 0.9 0.036 2.11 4.12 1.00 Farnesol (E)(E) 4735 1.28 0.046 1.00 1.42 5.87 7.80 1.00 Farnesol (E)(Z) 4660 1.26 0.046 1.52 1.72 5.86 6.10 1.00 Farnesol (Z)(E) 4630 1.305 0.046 1.52 5.64 5.69 1.00 Farnesol (Z)(Z) 4530 1.307 0.043 8.08 8.23 1.00 Galaxolide (Cis) 4640 2.11 0.065 0.75 5.69 6.10 0.75 Galaxolide (Trans) 4655 2.085 0.065 0.75 5.64 5.86 7.24 0.75 Geranial 2940 1.295 0.045 0.51 0.51 Geraniol 3305 0.91 0.036 9.11 1.00 Geranyl Acetate 3020 1.76 0.056 1.54 3.48 6.39 1.00 Hexadecanolide 4765 2.5 0.078 6.58 7.80 10.79 1.00 Hexyl Cinnamic Aldehyde (E) 4750 1.43 0.050 1.42 4.78 6.58 7.12 1.00 Hydroxycitronellal 3600 0.84 0.036 1.00 Hydroxyisohexyl 3-cyclohexene 5040 0.975 0.039 1.47 1.00 carboxaldehyde (Cyclohexal/Lyral major) Hydroxyisohexyl 3-cyclohexene 5010 0.97 0.039 1.47 3.52 1.00 carboxaldehyde (Cyclohexal/Lyral minor) Iso E Super Alpha 4135 2.145 0.066 9.59 1.00 Iso E Super Beta 3940 2.29 0.074 1.47 1.00 Iso E Super Gamma 3995 2.25 0.069 1.00 Iso E Super minor 3910 2.29 0.067 1.47 5.19 5.51 12.28 1.00 Isoeugenol (E) 4730 0.695 0.032 5.80 5.87 7.12 1.00 Isoeugenol (Z) 4490 0.715 0.033 2.11 6.05 1.00 Isoeugenyl Acetate 4915 0.875 0.035 0.49 3.34 0.49 Lilial 3905 1.475 0.049 1.34 5.51 7.17 1.00 Limonene 1070 2.72 0.075 1.00 Linalool 2305 1.12 0.040 1.00 Linalyl Acetate 2340 2.02 0.062 1.00 Majantol 4140 0.905 0.036 9.59 1.00 Menthol 2620 1.25 0.044 1.82 5.32 1.00 Methoxycoumarin-7 6145 0.805 0.038 1.00 Methyl Eugenol 3815 1.01 0.038 1.00 Methyl Heptine Carbonate 2665 1.21 0.042 4.85 1.00 Methyl Octine Carbonate 3000 1.33 0.046 3.48 5.17 1.00 Methyl Salicylate 3090 0.95 0.036 4.52 1.00 Neral 2770 1.34 0.046 2.46 6.29 1.00 n-pentyl isopentyl phthalate 5830 1.545 0.054 1.00 Phenyl Acetaldehyde 2650 0.755 0.032 4.85 5.32 1.00 Pinene Alpha 605 2.595 0.075 1.00 Pinene Beta 805 2.745 0.078 1.00 Propylidene Phthalide 3-(E) 4925 0.88 0.036 0.49 3.21 0.49 Propylidene Phthalide 3-(Z) 5195 0.86 0.037 0.76 4.32 0.76 Salicylaldehyde 2770 0.72 0.032 3.94 6.29 1.00 Santalol Alpha 4715 1.255 0.045 1.00 1.89 5.80 1.00 Santalol Beta 4925 1.205 0.043 3.21 3.34 1.00 Sclareol 6695 2.195 0.070 1.00 Terpinene Alpha 1010 2.7 0.074 1.00 Terpineol Alpha 2820 1.14 0.042 0.50 6.98 0.50 Terpineol Beta cis 2590 1.135 0.040 1.82 1.00 Terpineol Beta trans 2765 1.075 0.039 1.52 2.01 2.46 3.94 7.85 1.00 Terpineol Delta 2735 1.115 0.042 0.95 1.52 7.20 0.95 Terpineol Gamma 2830 1.15 0.042 0.50 6.84 0.50 Terpinolene 1350 2.72 0.075 1.00 Vanillin 5260 0.515 0.030 1.00

(19) TABLE-US-00006 TABLE 6 Experimental data for Rtx-17 × Wax stationary phase combination (Example 5) TC List of targets .sup.1tr .sup.2tr .sup.2Width Rs.sub.2D 1 Rs.sub.2D 2 Rs.sub.2D 2 Rs.sub.2D 4 Rs.sub.2D 5 SE.sub.2D Acetyl Cedrene (main isomer) 4375 0.84 0.0424 1.98 1.00 Alpha Isomethylionone 3245 0.77 0.0409 1.00 Amyl Cinnamic Alcohol (E) 4215 1.89 0.0749 1.36 2.52 4.64 1.00 Amyl Cinnamic Aldehyde (E) 4085 1.09 0.0503 1.62 2.19 2.43 4.45 1.00 Amyl Salicylate (ISO-) 3550 1.01 0.0452 13.64 1.00 Amyl Salicylate (N-) 3710 1.04 0.0459 4.97 1.00 Anethole Trans (E) 2770 1.105 0.0469 1.81 1.00 Anisyl Alcohol 2985 3.8 0.1346 12.12 14.13 1.00 Benzaldehyde 1465 1.435 0.0580 1.00 Benzyl Alcohol 1775 4.275 0.1502 1.00 Benzyl Benzoate 4730 1.51 0.0614 1.00 Benzyl Cinnamate (E) 5730 3.085 0.1144 1.23 1.00 Benzyl Cyanide 2430 2.26 0.0858 8.05 1.00 Benzyl Salicylate 5010 1.66 0.0650 1.00 Camphor 2100 0.77 0.0426 4.08 1.00 Carvone 2580 1.01 0.0468 0.42 0.42 Caryophyllene Beta 2865 0.525 0.0325 2.14 2.71 1.00 Cinnamic Alcohol (E) 3030 3.635 0.1304 11.32 11.70 12.54 13.11 1.00 Cinnamic Aldehyde (E) 2940 1.865 0.0728 7.40 1.00 Citronellol 2210 1.52 0.0635 2.05 1.00 Coumarin 3815 2.455 0.0939 5.77 1.00 Damascenone Beta 3035 0.85 0.0438 0.70 1.88 1.96 12.54 0.70 Damascone Alpha (E) 3030 0.78 0.0404 0.70 2.32 2.60 13.11 0.70 Damascone Alpha (Z) 2845 0.695 0.0378 0.80 2.14 0.80 Damascone Beta (E) 3115 0.78 0.0409 1.00 Damascone Beta (Z) 2990 0.705 0.0372 2.84 14.13 1.00 Damascone Delta cis/trans 2925 0.795 0.0411 1.61 7.40 1.00 Damascone Delta trans/cis 2725 0.71 0.0388 1.51 1.00 Damascone Delta trans/trans 2830 0.725 0.0359 0.80 0.80 Di Iso-Butyl Phthalate 4815 1.09 0.0487 1.00 Di isopentyl phthalate 5365 1.28 0.0573 1.00 Di Isopropyl Phthalate 4200 1.155 0.0509 2.26 3.37 3.45 4.64 1.00 Di n-Butyl Phthalate 5135 1.155 0.0513 1.00 Di n-pentyl phthalate 5615 1.665 0.0686 1.00 Dicyclohexyl phthalate 7095 3.9 0.1302 1.00 Diethyl Hexyl Phthalate 6680 2.935 0.1212 1.00 Diethyl Phthalate 4105 1.4 0.0590 0.84 2.43 4.58 0.84 Dimethyl Benzyl Carbinyl 2780 0.9 0.0455 1.81 1.00 Acetate Dimethyl Phthalate 3700 1.765 0.0691 4.97 1.00 Ebanol 1 3005 1 0.0472 1.96 2.32 2.84 11.70 12.12 1.00 Ebanol 2 3050 1.055 0.0490 1.88 2.60 7.64 11.32 1.00 Estragol 2335 0.995 0.0440 1.16 1.00 Eugenol 3075 2.37 0.0878 7.64 1.00 Eugenyl acetate 3825 1.35 0.0568 5.77 1.00 Farnesol (E)(E) 4095 1.3 0.0563 0.84 1.62 3.14 3.80 0.84 Farnesol (E)(Z) 4020 1.31 0.0573 0.25 1.19 0.25 Farnesol (Z)(E) 4015 1.31 0.0573 0.25 1.06 4.36 0.25 Farnesol (Z)(Z) 3925 1.12 0.0477 3.24 1.00 Galaxolide (Cis) 4670 0.78 0.0410 0.49 0.49 Galaxolide (Trans) 4680 0.78 0.0416 0.49 0.49 Geranial 2580 0.96 0.0469 0.42 0.42 Geraniol 2390 1.68 0.0675 1.78 1.00 Geranyl Acetate 2895 0.73 0.0380 1.61 2.71 1.00 Hexadecanolide 4850 0.8 0.0418 10.54 1.00 Hexyl Cinnamic Aldehyde (E) 4380 1.07 0.0495 1.98 1.00 Hydroxycitronellal 2675 1.72 0.0688 1.00 Hydroxyisohexyl 3-cyclohexene 4205 1.66 0.0671 1.16 1.23 1.36 3.37 1.00 carboxaldehyde (Cyclohexal/Lyral major) Hydroxyisohexyl 3-cyclohexene 4180 1.65 0.0666 1.23 1.30 1.46 3.45 1.00 carboxaldehyde (Cyclohexal/Lyral minor) Iso E Super Alpha 4080 0.835 0.0414 2.19 3.80 4.58 6.52 1.00 Iso E Super Beta 3960 0.77 0.0414 1.23 1.25 1.00 Iso E Super Gamma 3985 0.795 0.0411 1.25 4.36 5.20 1.00 Iso E Super minor 3935 0.765 0.0392 1.23 3.24 1.00 Isoeugenol (E) 3485 2.575 0.0945 1.00 Isoeugenol (Z) 3310 2.375 0.0803 11.56 1.00 Isoeugenyl Acetate 4160 1.51 0.0615 1.30 1.00 Lilial 3640 0.93 0.0452 1.00 Limonene 1240 0.435 0.0368 1.00 Linalool 1630 1.215 0.0534 1.00 Linalyl Acetate 2265 0.675 0.0368 1.00 Majantol 3205 1.785 0.0707 1.00 Menthol 1995 1.22 0.0532 1.00 Methoxycoumarin-7 4865 2.71 0.1007 10.54 1.00 Methyl Eugenol 3315 1.1 0.0495 11.56 1.00 Methyl Heptine Carbonate 2345 0.88 0.0421 1.16 1.00 Methyl Octine Carbonate 2720 0.865 0.0429 1.51 1.00 Methyl Salicylate 2390 1.4 0.0556 1.78 1.00 Neral 2440 0.925 0.0444 8.05 1.00 n-pentyl isopentyl phthalate 5485 1.455 0.0625 1.00 Phenyl Acetaldehyde 1865 1.475 0.0626 1.00 Pinene Alpha 825 0.285 0.0310 1.00 Pinene Beta 1040 0.35 0.0346 1.00 Propylidene Phthalide 3-(E) 4070 1.77 0.0714 3.14 4.45 6.52 1.00 Propylidene Phthalide 3-(Z) 4290 1.895 0.0721 1.00 Salicylaldehyde 1815 1.84 0.0692 1.00 Santalol Alpha 4005 1.45 0.0595 1.06 1.19 5.20 1.00 Santalol Beta 4200 1.475 0.0603 1.16 1.46 2.26 2.52 1.00 Sclareol 5745 2.8 0.1114 1.23 1.00 Terpinene Alpha 1205 0.415 0.0362 1.00 Terpineol Alpha 2175 1.245 0.0536 0.98 0.98 Terpineol Beta cis 1940 1.24 0.0536 1.00 Terpineol Beta trans 2060 1.33 0.0530 1.58 1.00 Terpineol Delta 2090 1.255 0.0513 1.58 4.08 1.00 Terpineol Gamma 2195 1.235 0.0534 0.98 2.05 0.98 Terpinolene 1545 0.48 0.0348 1.00 Vanillin 3540 4.595 0.1610 13.64 1.00

(20) TABLE-US-00007 TABLE 7 Experimental data for VF35-MS × Wax stationary phase combination (Example 6) TC List of targets .sup.1tr .sup.2tr .sup.2Width Rs.sub.2D 1 Rs.sub.2D 2 Rs.sub.2D 2 Rs.sub.2D 4 Rs.sub.2D 5 SE.sub.2D Acetyl Cedrene (main isomer) 4470 0.695 0.038827 2.21 1.00 Alpha Isomethylionone 3375 0.61 0.036351 11.16 1.00 Amyl Cinnamic Alcohol (E) 4280 1.675 0.061175 0.79 1.50 3.21 0.79 Amyl Cinnamic Aldehyde (E) 4150 0.94 0.045905 1.35 1.38 2.38 3.08 3.51 1.00 Amyl Salicylate (ISO-) 3665 0.825 0.040867 6.14 1.00 Amyl Salicylate (N-) 3825 0.85 0.042853 3.27 1.00 Anethole Trans (E) 2820 0.965 0.045055 2.35 4.06 1.00 Anisyl Alcohol 3000 3.624 0.13571 14.02 1.00 Benzaldehyde 1510 1.285 0.057839 1.00 Benzyl Alcohol 1820 3.984 0.142 1.00 Benzyl Benzoate 4745 1.38 0.059077 5.94 6.00 1.00 Benzyl Cinnamate (E) 5740 2.175 0.086254 1.00 Benzyl Cyanide 2435 2.15 0.084839 5.37 8.23 8.96 10.91 1.00 Benzyl Salicylate 5035 1.515 0.061639 1.00 Camphor 2200 0.62 0.040015 3.77 4.24 1.00 Carvone 2640 0.86 0.043668 1.35 1.00 Caryophyllene Beta 3050 0.38 0.029971 3.12 15.28 1.00 Cinnamic Alcohol (E) 3040 3.49 0.12971 13.39 13.92 15.28 1.00 Cinnamic Aldehyde (E) 2945 1.755 0.072103 8.73 1.00 Citronellol 2350 1.225 0.05472 1.00 Coumarin 3775 2.42 0.094431 1.00 Damascenone Beta 3125 0.7 0.039164 0.74 0.76 1.99 9.29 0.56 Damascone Alpha (E) 3130 0.63 0.037497 0.75 0.76 2.13 9.89 0.57 Damascone Alpha (Z) 2955 0.56 0.03537 8.73 1.00 Damascone Beta (E) 3220 0.63 0.037841 2.24 1.00 Damascone Beta (Z) 3095 0.57 0.036877 1.26 1.99 10.39 1.00 Damascone Delta cis/trans 3115 0.645 0.038025 0.74 0.75 1.26 9.74 0.56 Damascone Delta trans/cis 2845 0.565 0.036046 2.13 2.15 4.06 1.00 Damascone Delta trans/trans 3035 0.64 0.037202 1.15 3.12 13.39 1.00 Di Iso-Butyl Phthalate 4880 0.94 0.045613 1.00 Di isopentyl phthalate 5435 0.97 0.046779 1.00 Di Isopropyl Phthalate 4245 1.02 0.048296 1.53 3.16 3.34 1.00 Di n-Butyl Phthalate 5190 1.015 0.04802 1.00 Di n-pentyl phthalate 5675 1.2 0.05484 1.00 Dicyclohexyl phthalate 7010 3.125 0.14422 1.00 Diethyl Hexyl Phthalate 6585 1.64 0.060233 1.00 Diethyl Phthalate 4120 1.285 0.054237 0.71 1.68 1.70 3.08 5.56 0.71 Dimethyl Benzyl Carbinyl 2865 0.755 0.042792 2.13 1.00 Acetate Dimethyl Phthalate 3685 1.675 0.069177 6.14 1.00 Ebanol 1 3160 0.785 0.041446 2.13 1.00 Ebanol 2 3200 0.835 0.041854 2.24 1.00 Estragol 2410 0.84 0.04148 1.60 3.36 8.23 1.00 Eugenol 3120 2.135 0.082054 9.29 9.74 9.89 10.39 1.00 Eugenyl acetate 3830 1.255 0.054525 3.27 1.00 Farnesol (E)(E) 4215 1.075 0.0498 1.53 2.98 3.85 1.00 Farnesol (E)(Z) 4140 1.1 0.051734 0.29 1.03 1.38 1.68 2.45 0.29 Farnesol (Z)(E) 4135 1.08 0.050734 0.29 1.00 1.35 1.70 2.71 0.29 Farnesol (Z)(Z) 4030 1.04 0.047734 4.00 1.00 Galaxolide (Cis) 4750 0.65 0.037368 0.74 5.94 0.74 Galaxolide (Trans) 4765 0.65 0.037646 0.74 6.00 0.74 Geranial 2665 0.8 0.041155 1.35 1.00 Geraniol 2505 1.395 0.060047 5.01 1.00 Geranyl Acetate 3015 0.585 0.034552 1.15 13.92 14.02 1.00 Hexadecanolide 4955 0.65 0.037108 1.00 Hexyl Cinnamic Aldehyde (E) 4455 0.915 0.04388 2.21 1.00 Hydroxycitronellal 2765 1.47 0.062564 1.00 Hydroxyisohexyl 3-cyclohexene 4265 1.47 0.062262 1.23 1.50 2.24 3.34 1.00 carboxaldehyde (Cyclohexal/Lyral major) Hydroxyisohexyl 3-cyclohexene 4240 1.455 0.059895 1.23 2.98 3.16 1.00 carboxaldehyde (Cyclohexal/Lyral minor) Iso E Super Alpha 4190 0.675 0.036123 3.85 6.08 1.00 Iso E Super Beta 4075 0.62 0.037266 1.23 1.25 7.59 1.00 Iso E Super Gamma 4100 0.645 0.037522 1.25 4.96 5.56 7.45 1.00 Iso E Super minor 4050 0.615 0.038151 1.23 4.00 7.70 1.00 Isoeugenol (E) 3520 2.355 0.089013 6.92 1.00 Isoeugenol (Z) 3350 2.155 0.072906 7.59 11.16 1.00 Isoeugenyl Acetate 4165 1.4 0.059352 2.45 2.71 3.51 6.08 1.00 Lilial 3720 0.785 0.042075 1.00 Limonene 1400 0.3 0.038526 1.00 Linalool 1775 0.965 0.047271 1.00 Linalyl Acetate 2405 0.52 0.033467 2.75 3.36 10.91 1.00 Majantol 3290 1.535 0.065928 1.00 Menthol 2140 0.965 0.046888 1.00 Methoxycoumarin-7 4805 2.72 0.10329 1.00 Methyl Eugenol 3335 0.995 0.047454 7.59 1.00 Methyl Heptine Carbonate 2435 0.735 0.039 1.60 2.75 4.16 8.96 1.00 Methyl Octine Carbonate 2815 0.715 0.038717 2.15 2.35 1.00 Methyl Salicylate 2455 1.215 0.054091 4.16 5.37 1.00 Neral 2530 0.77 0.04091 5.01 1.00 n-pentyl isopentyl phthalate 5555 1.065 0.050681 1.00 Phenyl Acetaldehyde 1895 1.335 0.061039 2.41 1.00 Pinene Alpha 970 0.18 0.029529 1.00 Pinene Beta 1195 0.23 0.0377 1.00 Propylidene Phthalide 3-(E) 4080 1.635 0.067658 7.45 7.59 7.70 1.00 Propylidene Phthalide 3-(Z) 4290 1.775 0.065563 0.79 2.24 3.58 0.79 Salicylaldehyde 1865 1.65 0.068457 2.41 1.00 Santalol Alpha 4125 1.195 0.052257 0.71 1.00 1.03 2.38 4.96 0.71 Santalol Beta 4305 1.235 0.055219 3.21 3.58 1.00 Sclareol 5815 1.975 0.080211 1.00 Terpinene Alpha 1350 0.285 0.038326 1.00 Terpineol Alpha 2290 1.03 0.048384 1.24 1.00 Terpineol Beta cis 2065 1.01 0.045621 1.00 Terpineol Beta trans 2180 1.1 0.051334 1.09 4.24 1.00 Terpineol Delta 2200 1.04 0.047463 1.09 3.77 1.00 Terpineol Gamma 2315 1.01 0.047373 1.24 1.00 Terpinolene 1695 0.35 0.033478 1.00 Vanillin 3520 4.545 0.15927 6.92 1.00

(21) TABLE-US-00008 TABLE 8 Example of clustering for Rtx5 × Wax stationary phase combination Classifi- Rs.sub.2D with cation Rs.sub.2D neighbouring # # Defined analytical targets .sup.1tr (s) .sup.2tr (s) <1 peaks SE.sub.2D  1 C1 TERPINEOL BETA 2009 0.956  1 0.78 0.78 TRANS  2 C1 TERPINEOL DELTA 2023 0.890  1 0.78 1.58 0.78  3 C2, C3 TERPINEOL ALPHA 2128 0.864  1 0.52 0.82 1.26 0.42  4 C2, C4, C5 ESTRAGOL 2135 0.810  1 0.52 0.54 0.79 0.22  5 C5 METHYL HEPTINE 2135 0.720  1 0.79 1.11 1.26 0.79 CARBONATE  6 C3, C4 TERPINEOL GAMMA 2149 0.830  1 0.54 0.82 1.11 0.45  7 C6 DAMASCONE DELTA 2842 0.567  1 0.93 1.29 0.93 TRANS/TRANS  8 C6 GERANYL ACETATE 2856 0.494  0 0.93 1.04 1.63 0.93  9 C7 DAMASCENONE 2870 0.646  1 0.90 1.29 1.49 0.90 10 C7, C8 DAMASCONE DELTA 2891 0.600  1 0.84 0.90 1.04 0.76 CIS/TRANS 11 C8 DAMASCONE ALPHA E 2912 0.567  1 0.84 1.20 4.35 0.84 12 C9 ISO E SUPER MINOR 3864 0.547  1 0.77 3.31 5.05 0.77 13 C9 ISO E SUPER BETA 3885 0.547  1 0.77 1.05 3.09 0.77 14 C10 FARNESOL EZ 3983 0.860  1 0.00 2.38 5.08 0.00 15 C10 FARNESOL ZE 3983 0.860  1 0.00 2.30 5.14 0.00 16 C11 GALAXOLIDE 1 4459 0.613  1 0.26 0.26 17 C11 GALAXOLIDE 2 4466 0.619  1 0.26 0.26 18 Sum defined analytical 17 targets with Rs.sub.2D < 1

(22) TABLE-US-00009 TABLE 9 List of clustered targets Clustered Defined Rtx-5Sil × Rtx-5Sil × Rtx- Wax × Rtx- Rtx-17Sil × VF35 × analytical targets Wax 17Sil 5Sil Wax Wax Amyl Cinnamic Alcohol (E) x x Anisyl Alcohol x Carvone x x Cinnamic Alcohol (E) x Damascenone Beta x x x Damascone Alpha (E) x x x x x Damascone Alpha (Z) x Damascone Beta (Z) x Damascone Delta cis/trans x x x x Damascone Delta trans/trans x x Diethyl Phthalate x x Estragol x x x Farnesol (E)(E) x Farnesol (E)(Z) x x x x Farnesol (Z)(E) x x x x Galaxolide (Cis) x x x x x Galaxolide (Trans) x x x x x Geranial x x Geranyl Acetate x Iso E Super Beta x Iso E Super minor x Isoeugenyl Acetate x Methyl Heptine Carbonate x x Phenyl Acetaldehyde x Propylidene Phthalide 3-(E) x Propylidene Phthalide 3-(Z) x x Salicylaldehyde x Terpineol Alpha x x x x Terpineol Beta trans x x Terpineol Delta x x x Terpineol Gamma x x x x

(23) TABLE-US-00010 TABLE 10 Results and parameters of Equations 1, 2, 3, 4 and 5. Rtx-5Sil × Rtx-5Sil × Wax × Rtx- Rtx-17Sil × VF35 × Wax Rtx-17Sil 5Sil Wax Wax Parameters in Equations 3 and 4 Number of defined analytical 17 15 16 14 11 targets neighbor peaks with Rs.sub.2D < 1, i.e. clustered defined analytical targets Number of singletons, i.e. resolved 78 80 79 81 84 defined analytical targets Value of SE.sub.2D 92.5 92.7 93.3 94.7 95.5 Value of .sup.nSE.sub.2D 7.5 7.3 6.7 5.3 4.5 Parameters in Equation 5, 6 and 7 First eluting target on first 1043 1090 605 825 970 dimension (.sup.1t.sub.first) Last eluting target on first 6251 6300 6905 7095 7010 dimension (.sup.1t.sub.last) Modulation period (Pmod) 7 5 5 5 5 Observed first dimension peaks 186 261 315 314 302 capacity (.sup.1,obsnc) First eluting target on second 0.16 0.80 0.49 0.29 0.18 dimension (.sup.2t.sub.first) Last eluting target on second 6.62 4.14 4.42 4.60 4.55 dimension (.sup.2t.sub.last) a in Equation 7 0.009545 0.004256 0.005142 0.00798 0.00844 b in Equation 7 0.006944 0.018916 0.004442 0.006423 0.006174 Observed second dimension 26.2 16.2 24.5 22.7 23.5 peaks capacity (.sup.2,obsnc) Observed 2D dimension peaks 3097 2691 4913 4521 4527 capacity (.sup.obsnc.sub.2D)

Example 7: Clustering of Ingredients

(24) Pictorial representations of separation patterns of close defined analytical targets obtained with 2D GC set-ups in accordance with Examples 2 through 6 were prepared and are shown in FIGS. 2 through 5.