Comparison of “Weird and Wild” Jelly Bean Flavors Using HS SPME Gas Chromatography Mass Spectrometry
Joseph E. Binkley, David E. Alonso, Jonathan D. Byer, Christina Kelly, and Lorne M. Fell | LECO Corporation, Saint Joseph, MI
Introduction
Methods
Results
Bring Your Children to Work Day is a national event in the United States which often
excludes children with parents in the sciences due to lab safety protocols. This poster
details a safe experiment which was designed to create interest in the sciences for all
ages, while also demonstrating the capabilities of a new benchtop Time-of-Flight GC-MS,
to effectively differentiate some very exotic flavor profiles in store-purchased jelly beans.
A portion of a single jelly bean was placed into a 20 mL HS vial along with 5 mL of HPLC
grade H2O, and 1g of NaCl. A 1 cm PDMS/Carboxen/DVB SPME fiber was used to extract
aroma compounds from the headspace of each jelly bean and deliver them to the
GC–MS for analysis. An Rtx-200 MS column was used for the chromatographic separation.
The TOFMS data were acquired from 30 to 500 m/z at 20 spectra/second.
The benchtop time-of-flight GC-MS data was used to differentiate the visually identical jelly beans based on the components detected and identified in their headspace. The data was compiled into tables
with key analytes, and their taste/odor descriptors, so that the kids could use the information to influence their decision when making their second-round jelly bean selections for tasting.
43.02
1.4e7
1.2e7
93.04
80
100
120
140
41.04
85
41
1000
900
800
700
600
500
400
300
200
100
0
M/Z
55
121
93
60
40
55.04
79
43
88
60
73
0
1.5e9
Library Hit - Similarity: 977 - Library: replib - ç-Decalactone, Abundance
51
71
43
41
0.2e8
40
60
80
100
120
140
160
180
200
114.03
99.01
73.00
81.05
46.99
73
41
81
99
114
39
62
45
140
1.8e9
400
450
15
17.5
20
17.5
20
136.08
4e6
3e6
2e6
1e6
0
Library Hit - Similarity: 945 - Library: replib - Pyrazine, tetramethyl-, Abundance
117
132
350
300
12.5
TIC HS SPME Peach
Barf
8.4e8
43
250
200
150
10
Compound Name & Descriptors
2-nonanone (cheesy, green, fruity, dairy, dirty)
diallyl sulfide (sulfurous, onion-garlic, horseradish)
2-undecanone (creamy cheese like notes)
hexanoic acid (sour, fatty, sweat, cheesy)
octanoic acid (rancid, soapy, cheesy, fatty)
carvacrol (spicy, herbal, medicinal)
7.2e8
100
7.5
TIC HS SPME Barf
Peach
Library Hit - Similarity: 923 - Library: mainlib - Dimethylbenzylcarbinyl acetate, Abundance
50
5
Peak True - sample "HS SPME Chocolate Pudding", Pyrazine, tetramethyl-, at 10.9723 min, Area (Counts)
54.04
5e6
Peak True - sample "HS SPME Berry Blue", Dimethylbenzylcarbinyl acetate, at 12.8965 min, Area (Counts)
43.02
1.0e8
0.9e8
0.8e8
0.7e8
0.6e8
0.5e8
0.4e8
0.3e8
0.2e8
0.1e8
0
1000
900
800
700
600
500
400
300
200
100
0
M/Z
2.5
Compound Name & Descriptors
isoamyl butyrate (fruity, green, apricot, pear, green apple)
hexyl acetate (fruity, fresh, sweet banana)
geranyl isobutyrate (peach, sweet, floral)
gamma-Dodecalactone (peach, sweet fruity)
gamma-decalactone (fruity, creamy, peach)
91
136
93
105
107
2.1e9
160
140
120
39.03
41.04
62.01
47
20
59
2.4e9
77
79
65
67
17.5
Compound Name & Descriptors
2-methyl-benzenethiol (meaty, sulferous, egg)
dimethyl sulfide (sulfery, onion, cabbage)
dimethyl disulfide (sulferous cabbage, malt, cream)
s-(methylthio) butyrate (sulfury, cheese, putrid, musty, limberger-type cheese)
39
53
12.5
15
TIC HS SPME Butter Popcorn
0
Time (min)
59.04
105.06
107.07
65.03
51.02
53.04
136.10
77.03
79.04
39.04
10
Compound Name & Descriptors
2,3-pentanedione (toasted, buttery, creamy, caramellic)
Butyl butyrolactate (creamy, buttery, buttermilk)
2-acetyl pyridine (popcorn, heavy corn)
gamma decalactone (coconut, buttery, sweet)
2.7e9
121
100
5
7.5
TIC HS SPME Rotten Eggs
Rotten Egg
0
80
2.5
Butter Popcorn
0.2e7
60
120
6.0e8
500
1000
900
800
700
600
500
400
300
200
100
0
M/Z
136
20
Library Hit - Similarity: 907 - Library: replib - Terpinolene, Abundance
40
100
42.04
17.5
0
Time (min)
Peak True - sample "HS SPME Lime", Terpinolene, at 9.52912 min, Area (Counts)
93.06
1.6e7
121.08
1.4e7
51
80
39.03
Compound Name & Descriptors
hexanoic acid (sour, fatty, sweat, cheesy)
octanoic acid (rancid, cheesy, oily)
isovaleric acid (sour, stinky feet, sweaty, cheese)
2-methyl-pentanoic acid (sour, cheese)
1000
900
800
700
600
500
400
300
200
100
0
M/Z
60
54
Compound Name & Descriptors
isobutyl acetate (sweet, fruity, tropical)
ethyl butyrate (fruity, pineapple, sweet)
3-methyl-1-butanol-acetate (sweet, fruity, banana)
d-limonene (sweet, orange, citrus)
linalool (citrus, floral, sweet, orange, lemon)
(E)-citral (citrus, lemon)
0.4e7
40
42
12.5
15
TIC HS SPME Tutti Fruitti
Stinky Socks
0.8e7
140
39
10
Tutti Fruitti
0.6e7
0.3e9
120
100
80
60
40
1000
900
800
700
600
500
400
300
200
100
0
M/Z
140
120
91.03
100
80
60
40
5
7.5
TIC HS SPME Stinky Socks
1.2e7
0
Library Hit - Similarity: 916 - Library: replib - Diallyl sulfide, Abundance
87
39
45
41
43
0.3e9
1e6
47
60
Library Hit - Similarity: 885 - Library: replib - Isovaleric acid, Abundance
1.0e7
34.96
1000
900
800
700
600
500
400
300
200
100
0
M/Z
45
87.03
74.02
Library Hit - Similarity: 977 - Library: replib - Dimethyl sulfide, Abundance
0.6e9
0
1000
900
800
700
600
500
400
300
200
100
0
M/Z
0.6e9
0
1e7
2.5
44.98
2e6
2e7
39.02
41.04
45.02 43.04
3e7
0.3e9
44.98
3e7
Peak True - sample "HS SPME Barf", Diallyl sulfide, at 7.99876 min, Area (Counts)
1e7
4e7
0.6e9
0.9e9
Peak True - sample "HS SPME Rotten Eggs", Dimethyl sulfide, at 1.98721 min, Area (Counts)
46.99
4e7
0.9e9
2e7
2.1e9
0.4e8
1.2e9
0.9e9
2.4e9
0.6e8
1.2e9
5e7
2.7e9
0.8e8
1000
900
800
700
600
500
400
300
200
100
0
M/Z
Peak True - sample "HS SPME Stinky Socks", Isovaleric acid, at 12.3157 min, Area (Counts)
60.01
The kids were then able to load the samples into the autosampler of the GC-MS system,
and start the sample queue on their own. The jelly beans were analyzed on the Pegasus
BT under the conditions shown below in Table II.
1.0e8
0
1.5e9
1.2e9
0
Time (min)
1.2e8
35
Tutti-Fruitti & Stinky Socks
Buttered Popcorn & Rotten Egg
Peach and Barf
Lime & Lawn Clippings
Berry Blue and Toothpaste
Chocolate Pudding & Canned Dog Food
1.5e9
1.4e8
Library Hit - Similarity: 918 - Library: replib - 2-Acetylpyridine, Abundance
140
120
100
80
60
1.6e8
117.05
132.06
Visually Similar Jelly Bean Pairs
1.8e9
40
45
Table I. Description of Jelly Bean Pairs
39
2.1e9
1000
900
800
700
600
500
400
300
200
100
0
M/Z
85.01
1.8e8
0.2e7
1.8e9
Library Hit - Similarity: 956 - Library: mainlib - Ethyl butyrate, Abundance
Peak True - sample "HS SPME Peach", ç-Decalactone, at 14.9241 min, Area (Counts)
39.03
0.4e7
0
1.8e9
39
60.03
88.06
0.8e7
0.6e7
73.04
0.2e8
45.05
0.4e8
39.04
0.6e8
41.06
1.0e7
121.03
1.0e8
0.8e8
2.4e9
They were then asked to taste their selection to see if they had “won” or “lost” by
selecting an appealing vs. appalling jelly bean flavor. It was evident that selections
based on visual appearance of the jelly beans alone led to random results during the
taste tests. Example responses from our willing participants are shown in the photos
below.
Peak True - sample "HS SPME Butter Popcorn", 2-Acetylpyridine, at 11.9238 min, Area (Counts)
79.02
1.6e7
51.02
2.7e9
2.1e9
Peak True - sample "HS SPME Tutti Fruitti", Ethyl butyrate, at 6.28611 min, Area (Counts)
43.07
71.06
As part of the experiment, kids participated in a game in which they took turns selecting
a jelly bean from one of the matching pairs shown in Table I below.
The Total Ion Chromatograms (TICs) with tables containing the key differentiating ingredients for each Jelly Bean type are shown below. Each chromatogram also includes a deconvoluted mass spectrum
from one of the key taste/odor analytes, and its NIST library match with similarity score, which were used to tentatively identify them.
80
60
40
100
120
140
160
180
1.8e9
1.5e9
The kids participated in preparing the jelly beans for a HS-SPME GC-MS experiment that
would provide the data used to influence their selections. The details of the sample
preparation and subsequent GC-MS analyses are shown in the Methods section.
Figure 1. Pegasus BT
0
Time (min)
Table II. GC-MS Instrument Conditions
Gas Chromatograph
Injection
Carrier Gas
Column
Oven Program
Transfer Line
Mass Spectrometer
Ion Source Temperature
Mass Range
Acquisition Rate
Agilent 7890 with LECO L-PAL3 Autosampler
2 min SPME desorption, Split 10:1 at 250˚C
He @ 1.0 ml/min, Constant Flow
Rtx-200 MS, 30 m x 0.25 mm i.d. x 0.25 µm coating (Restek)
5 min at 35°C, ramp 20°C/min to 240°C, hold 5 min
250°C
LECO Pegasus BT
250°C
30-500 m/z
20 spectra/s
2.5
100
7.5
5
TIC HS SPME Grass Clippings
10
12.5
TIC HS SPME Lime
15
Lime
Grass Clippings
Compound Name & Descriptors
D-Limonene (citrus, orange, fresh, sweet)
ç-Terpinene (lemon/lime, tropical)
terpinolene (fresh, citrus, lemon and lime-like, terpy)
octanal (green with peely citrus orange)
Compound Name & Descriptors
(Z)-3-hexen-1-ol (fresh green cut grass)
estragole (sweet, phenolic, weedy)
benzyl alcohol (floral, rose)
17.5
20
0
Time (min)
225.98
85.00
68.98
51.02
58.99
39.03
150
100
120
140
160
226
155
85
43
51
2.5
80
1.2e8
108
93
60
77
79
0.3e9
120
67
69
80
150.09
82
54
1000
900
800
700
600
500
400
300
200
100
0
M/Z
39
82
55
67
0.6e9
53
57
60
2.4e8
0
Library Hit - Similarity: 952 - Library: replib - (-)-Carvone, Abundance
41
40
108.07
93.05
1e7
0
77.02
79.04
2e7
58
0.3e9
39
1000
900
800
700
600
500
400
300
200
100
0
M/Z
1e6
Library Hit - Similarity: 893 - Library: mainlib - Furan, 3,3'-dithiobis[2-methyl-, Abundance
113
1000
900
800
700
600
500
400
300
200
100
0
M/Z
175
200
125
150
100
50
75
69
0
Library Hit - Similarity: 923 - Library: replib - 3-Hexen-1-ol, (Z)-, Abundance
0.6e9
54.01
4e7
0.9e9
4e6
2e6
3e7
41.01
1e7
53.06
57.03
44.03
2e7
69.07
3e7
7e6
6e6
5e6
3e6
5e7
82.08
4e7
0.9e9
55.05
39.04
5e7
3.6e8
Peak True - sample "HS SPME Tooth Paste", (-)-Carvone, at 12.7556 min, Area (Counts)
81.99
6e7
58.01
65.01
67.02
1.2e9
Peak True - sample "HS SPME Grass Clippings", 3-Hexen-1-ol, (Z)-, at 10.2783 min, Area (Counts)
6e7
67.07
41.07
43.02
Peak True - sample "HS SPME Dog Food", bis(2-methyl-3-furyl) disulfide, at 14.9571 min, Area (Counts)
112.99
8e6
1.2e9
A second round of the game was started, and the kids were given an option to have
LECO’s Pegasus® BT GC-MS system “taste” the jelly beans first, prior to the kids making a
selection. The components identified by the GC-MS, and their respective taste and
odor descriptors, were used to aid in selecting jelly beans in this round.
4.8e8
1.5e9
225
180
7.5
5
TIC HS SPME Tooth Paste
10
15
12.5
TIC HS SPME Berry Blue
Berry Blue
Toothpaste
Compound Name & Descriptors
Linalool (citrus, orange, sweet)
ethyl nonanoate (fruity and tropical)
dimethylbenzylcarbinyl acetate (sweet, fruity, berry, jasmin)
ethyl butyrate (fruity, pineapple)
ethyl isovalerate (sweet, fruity, apple, pineapple)
ethyl hexanoate (sweet, pineapple, banana)
Compound Name & Descriptors
menthol (cooling, minty)
carvone (minty, spearmint)
methyl-salicylate (minty, wintergreen)
cinnamaldehyde (cinnamon, red hots, spicy)
Conclusions
With the use of the Pegasus BT data, the kids were able to predict the good vs bad flavored jelly
beans based on the published sensory descriptors for the analytes which were identified by GC-MS
in each of the jelly bean varieties.
The kids found the experiment exciting, and were exposed to analytical chemistry in a fun and
educational way.
17.5
20
0
Time (min)
2.5
7.5
5
TIC HS SPME Dog Food
10
15
12.5
TIC HS SPME Chocolate Pudding
Chocolate Pudding
Canned Dog Food
Compound Name & Descriptors
3-methlbutanal (chocolate, peach, fatty)
vanillin (creamy chocolate, sweet vanilla)
tetramethyl pyrazine (musty, nutty, chocolate coffee, cocoa)
Compound Name & Descriptors
1-octen-3-ol (mushroom, earthy, raw chicken, oily, fungal)
2-acetylthiazole (cornchip with musty background, popcorn, roasted peanuts)
2,4-decadienal (fatty, oily, chicken, fried, slight rancid tallow)
triacetin (creamy, with an oily mouth feel)
bis(2-methyl-3-furyl)disulfide (strong meaty, brothy, roasted savory, cooked onion, garlic and black pepper)