Shida Shen, Craig Whitehouse and Avinash Dalmia
1
PerkinElmer, Inc., 940 Winter Street, Waltham, MA USA (800) 762-4000 or (+1) 203 925-4602 www.perkinelmer.com Introduction 1 The enclosed DSA ion source was mounted to a PerkinElmer AxION 2 TOF mass spectrometer (MS). The integral multiple inlet reagent ion generator position was adjustable relative to the sampling and MS entrance. Reagent ion gas composition, flow rate and temperature, countercurrent heated gas flow rate and temperature, and purge gas flow rate were adjustable through software controls. Solid and liquid samples were introduced into the ion source individually or in batches. They were mounted on a four axis translator with sample position controlled through software. For all samples, nitrogen was used as the carrier gas. For samples with low proton affinity, different reagent ions were added as gas or nebulized and vaporized liquid to improve sample ionization efficiency. The reagent ion generator was operated in APCI mode as well for direct ionization of liquid and gas samples calibration solution. The sample target position was controlled using a four axis translator stage with three linear axis and one rotating axis. Different sample types were mounted on round or square sample holders . The reagent ion generator was mounted on a three axis translator to allow optimization of the exit position. Sample was heated through the heated gas delivered from the reagent ion generator . Gas temperature and flow rate was adjusted maximize signal. Performance of an Enclosed Atmospheric Pressure Direct Sample Analysis (DSA) Source Shida Shen, Craig Whitehouse and Avinash Dalmia A novel enclosed Direct Sample Analysis (DSA) ion source was developed for the direct analysis of solid, liquid and gas samples using Atmospheric Pressure Chemical Ionization and Electrospray charged droplet charge transfer. The enclosed ion source allows programmed control of the reagent ion population, carrier gas species, enthalpy transfer and voltages in ionization and sampling region. Gas entering the ion source during operation can be vented to an exhaust system to avoid exposing the user to vaporized sample. Voltages are applied to the sampling inlet electrodes without exposure to the user during operation. Improved ionization and sampling efficiencies result from a combination of optimized heated gas flow and electric fields in the source and ion transport regions. Experiments 3 Method 2 41.02 42.02 66.02 98.11 102.14 103.15 124.06 152.16 178.78 206.20 232.95 260.30 287.23 314.29 341.38 369.34 396.61 0 500000 1000000 1500000 2000000 2500000 3000000 3500000 0 50 100 150 200 250 300 350 400 450 Mass RET (255.67808) Amplitude m/z Curve 1 40.02 40.55 70.07 74.11 94.26 117.07 144.16 171.14 197.85 225.12 252.20 280.28 308.29 336.39 364.38 391.32 0 500000 1000000 1500000 2000000 2500000 3000000 3500000 0 50 100 150 200 250 300 350 400 450 Mass RET (07.38783) Amplitude m/z Curve 1 Diethylamine Triethylamine 40.03 45.04 55.53 72.09 87.02 97.09 123.11 147.11 157.82 163.14 164.15 175.93 194.12 212.15 230.05 248.17 266.20 284.21 0 250000 500000 750000 1000000 1250000 1500000 1750000 2000000 50 100 150 200 250 300 Mass RET (09.72716) Amplitude m/z Curve 1 Nicotine Gas Samples Cigarette Smoke Experiments 3 Solid Samples 40.01 40.53 64.96 90.05 121.01 122.02 139.02 152.05 163.02 190.06 195.07 196.07 234.76 241.03 265.11 297.11 355.05 361.07 411.20 441.08 473.20 0 500000 1000000 1500000 2000000 2500000 50 100 150 200 250 300 350 400 450 500 Mass RET (69.57083) Amplitude m/z Curve 1 Caffeine Acetaminophen Fragment of Aspirin M-H 2 O of Aspirin PainAway Tablet 40.01 43.00 45.02 53.00 78.05 115.02 121.02 121.07 122.02 149.01 150.01 157.03 163.02 197.07 198.06 203.08 227.06 277.11 278.11 308.11 339.10 361.07 369.13 399.11 429.13 459.15 0 500000 1000000 1500000 2000000 2500000 50 100 150 200 250 300 350 400 450 500 Mass RET (03.33833) Amplitude m/z Curve 1 M-H 2 O of Aspirin Fragment of Aspirin Baby Aspirin Tablet Powder Samples 286.15 300.12 301.21 302.22 309.11 309.20 316.20 323.12 337.25 338.25 339.01 339.12 339.25 345.27 352.28 359.26 369.13 370.13 371.13 371.31 372.09 372.32 379.27 387.23 0 2500 5000 7500 10000 12500 15000 290 300 310 320 330 340 350 360 370 380 390 400 Mass RET (02.49816) Amplitude m/z Curve 1 Bisdemethoxy Curcumin Demethoxy Curcumin Curcumin (MH + =369.13325) Turmeric Powder 43.98 56.01 59.05 63.04 91.05 138.01 195.10 252.16 271.20 289.21 290.21 311.18 368.24 424.86 485.29 549.59 577.41 578.42 579.42 606.39 666.46 724.59 780.79 852.74 913.59 0 50000 100000 150000 200000 250000 300000 350000 400000 0 100 200 300 400 500 600 700 800 900 1000 Mass RET (00.88150) Amplitude m/z Curve 1 Testosterone [M+H] + Dimer [2M+H] + Testosterone Powder 107.04 116.05 135.07 141.10 170.08 175.10 195.08 199.06 220.27 263.23 268.13 269.14 270.14 288.17 313.15 338.14 366.35 371.30 391.24 440.32 465.12 0 50000 100000 150000 200000 250000 300000 100 150 200 250 300 350 400 450 500 Mass RET (00.83816) Amplitude m/z Curve 1 Diethyl Stilbestrol [M+H] + Diethyl Stilbestrol Experiments 3 Liquid Samples Liquid Samples Are Dispensed onto a Mesh Target Prior to Running in the DSA Source. 45.03 51.02 78.98 112.04 151.11 209.02 216.10 217.10 218.10 248.04 287.16 329.18 371.10 410.22 450.20 490.02 530.21 570.27 609.38 0 50000 100000 150000 200000 250000 300000 350000 400000 450000 100 200 300 400 500 600 700 Mass GEN (04.32583:04.33583) Amplitude m/z Curve 1 42.03 43.02 45.03 51.02 56.01 57.02 59.05 81.07 114.05 149.02 153.09 216.09 217.09 218.09 219.09 256.25 277.15 280.25 282.27 284.29 338.33 340.34 379.27 418.37 457.29 496.18 535.50 574.41 613.52 654.15 0 5000 10000 15000 20000 25000 30000 35000 100 200 300 400 500 600 700 Mass RET (04.17116) Amplitude m/z Curve 1 100.07 114.09 136.02 149.03 151.07 172.13 211.09 216.10 218.10 256.27 279.17 280.27 282.28 284.30 290.97 365.18 369.36 371.11 400.26 438.46 476.38 518.30 553.54 591.60 638.64 674.63 0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000 6500 100 150 200 250 300 350 400 450 500 550 600 650 700 Mass RET (00.48783) Amplitude m/z Curve 1 199.17 200.17 201.02 201.18 202.18 203.06 203.09 205.09 207.05 207.16 208.14 209.11 211.13 211.16 213.09 213.16 214.18 215.19 216.10 216.19 217.18 218.10 219.06 219.11 221.15 223.08 223.15 225.14 227.10 227.20 228.20 229.07 229.21 231.11 0 100 200 300 400 500 600 700 800 900 200 205 210 215 220 225 230 Mass RET (01.70800) Amplitude m/z Curve 1 1000 ppb 10 ppb 100 ppb 3 ppb Atrazine in Tap Water 41.03 56.01 69.03 81.03 85.02 96.04 115.03 125.06 127.03 143.03 145.04 163.05 163.13 180.08 183.08 197.10 198.09 200.10 202.04 203.13 231.99 272.13 306.11 325.11 342.13 343.13 346.16 375.16 378.15 404.16 434.18 487.16 0 5000 10000 15000 20000 25000 30000 50 100 150 200 250 300 350 400 450 500 Mass RET (05.00800) Amplitude m/z Curve 1 Thiabendazole [M+H] + 1 ppm Thiabendazole spiked in apple juice 153.1287 283.2641 357.2999 397.3827 411.3984 575.5016 577.5180 601.5172 603.5331 605.5430 859.7679 0 5000 10000 15000 20000 25000 30000 35000 40000 0 100 200 300 400 500 600 700 800 900 1000 Mass GEN (14.25600:14.75600) Amplitude m/z Curve 1 [OO+H] + [OP+H] + [OS+H] + [LP+H] + Olive Oil Characterization 855.74 856.76 857.76 858.77 859.78 860.78 861.78 875.77 877.80 881.76 883.78 884.78 885.80 886.80 887.80 888.80 901.77 903.80 922.02 923.02 0 250 500 750 1000 1250 1500 1750 850 860 870 880 890 900 910 920 Mass GEN (14.25600:14.75600) Amplitude m/z Curve 1 [OOO+H] + [OLO+H] + [OPO+H] + [POL+H] + Zoom in 40.02 66.00 87.00 134.05 151.11 191.06 253.20 255.23 279.22 281.24 282.24 310.25 377.11 433.34 537.47 551.97 563.49 564.49 637.52 694.55 751.57 808.56 864.91 921.69 0 25000 50000 75000 100000 125000 150000 0 100 200 300 400 500 600 700 800 900 1000 Mass RET (02.47483) Amplitude m/z Curve 1 41.99 44.99 59.98 115.07 145.05 255.22 277.20 278.21 279.22 280.23 281.24 282.24 386.25 415.34 434.33 444.34 448.34 512.32 624.47 689.57 768.47 886.69 887.70 906.64 972.76 0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000 0 100 200 300 400 500 600 700 800 900 1000 Mass RET (05.82483) Amplitude m/z Curve 1 41.00 73.03 97.02 151.99 255.23 277.21 279.23 280.23 281.25 282.25 301.23 389.28 448.35 455.18 551.33 561.48 563.49 564.49 618.46 684.53 750.12 815.75 886.63 952.58 0 5000 10000 15000 20000 25000 30000 35000 40000 45000 0 100 200 300 400 500 600 700 800 900 1000 1100 Mass RET (96.13183) Amplitude m/z Curve 1 Olive Oil Vegetable Oil Canola Oil Oleic Oleic Oleic Palmitic Palmitic Palmitic Linoleic Linoleic Linoleic Linolenic Linolenic Palmitoleic Cooking Oil Other Applications 4 0 2500 5000 7500 10000 12500 15000 17500 20000 22500 304.125 304.150 304.175 304.200 304.225 304.250 304.275 304.300 16.5 17.0 17.5 18.0 18.5 19.0 19.5 20.0 20.5 BIC m/z (303.959:304.345) Amplitude m/z Time (min) Amplitude m/z $20 bill $5 bill $1 bill $100 bill “Hotness” of Peppers 251.18 268.20 276.17 292.81 304.16 308.23 309.22 324.08 326.25 339.27 364.24 367.27 382.29 384.30 385.30 398.31 419.32 425.32 436.34 442.34 443.35 452.30 480.37 483.36 500.38 0 1000 2000 3000 4000 5000 6000 7000 8000 9000 250 300 350 400 450 500 Mass RET (18.07366) Amplitude m/z Curve 1 242.28 258.11 274.16 290.14 304.15 305.16 323.15 326.25 339.20 354.91 384.30 388.15 391.29 394.22 404.20 420.19 439.23 442.34 455.25 471.20 487.36 0 5000 10000 15000 20000 25000 250 300 350 400 450 500 Mass RET (18.77358) Amplitude m/z Curve 1 Cocaine MH + =304.15432 Cocaine 19 times higher ! $20 bill $5 bill Trace Amount Cocaine on US Paper Currency 279.01 279.23 282.27 284.29 285.28 288.28 291.19 294.05 297.07 300.16 303.26 306.20 307.21 308.22 309.22 312.20 315.12 318.18 321.21 324.23 0 25000 50000 75000 100000 125000 150000 175000 200000 225000 280 285 290 295 300 305 310 315 320 325 330 Mass RET (02.48483) Amplitude m/z Curve 1 302.17 303.20 304.00 305.23 306.00 306.20 307.20 307.96 308.21 308.36 309.22 310.24 311.04 312.12 313.12 0 2500 5000 7500 10000 12500 15000 17500 20000 22500 302 303 304 305 306 307 308 309 310 311 312 313 314 Mass RET (04.11816) Amplitude m/z Curve 1 289.08 290.22 292.23 293.16 293.23 294.18 295.20 296.19 297.20 298.20 299.27 301.13 301.21 304.00 304.24 305.23 306.20 307.21 308.22 309.19 309.25 310.16 311.23 313.12 315.11 316.24 317.25 318.18 320.97 321.25 323.22 325.10 327.23 328.23 330.26 0 50 100 150 200 250 300 350 400 450 500 550 600 290 295 300 305 310 315 320 325 330 Mass RET (03.71816) Amplitude m/z Curve 1 Jalapeno Pepper Chilli Pepper Cubanelle Pepper Dihydro apsaicin Capsaicin Dihydro Capsaicin Dihydro Capsaicin Capsaicin Capsaicin Melatonin in Lazy Cakes 95.04 97.02 109.02 111.04 126.05 127.03 139.03 145.04 152.07 163.05 180.08 181.06 182.07 193.04 195.08 206.08 219.07 231.92 233.12 245.10 258.10 271.07 284.06 0 10000 20000 30000 40000 50000 60000 70000 100 125 150 175 200 225 250 275 300 Mass RET (00.47150) Amplitude m/z Curve 1 Melatonin MH+ = 233.1285 Conclusion 5 The DSA ion source with automated sample positioning allows multiple samples to be loaded and run in a sealed enclosure. Ions have been generated from solid, liquid and gas samples in both positive and negative ion polarity mode. Powder samples were run in small amounts loaded onto a melting point tube. The reagent ion generator is configured with multiple gas and a liquid inlet. The liquid is nebulized and vaporized allowing tight control of reagent ion concentration, such as water. The reagent ion generator configured with an internal corona discharge needle near the exit end can also be operated as an APCI inlet probe to directly ionize gas and nebulized and vaporized liquid samples. Calibration solution for accurate mass TOF MS was introduced as a liquid into the ion generator. Voltages applied to the mass spectrometer capillary entrance electrodes improve ion sampling efficiency compared to ions sampled using gas flow alone. The sealed enclosure prevents the user from being exposed to the samples being run. The source enclosure is purged with nitrogen gas and vented to a laboratory exhaust system. In all studies reported here, nitrogen was used as the carrier gas yielding high ionization efficiency for most of the samples run. For samples with low proton affinities, adding a reagent species such as ammonia improved ionization efficiency. Auxiliary Gas Inlet Nebulization Gas Inlet Liquid Inlet Heater N 2 Corona Needle Sample 02 ccs 2009 11 04 ee_1 260 240 220 200 180 160 140 120 100 80 m/z 8 16 24 32 40 48 56 64 72 80 88 96 Relative Intensity (%) 74 102 121 138 163 177 195 224 240 254 02 ccs 2009 11 04 ed_1 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 m/z 8 16 24 32 40 48 56 64 72 80 88 96 Relative Intensity (%) 73 87 110 121 138 152 167 195 207 227 Active ingredients (in each tablet) Acetaminophen 110 mg Aspirin 162 mg Salicylamide 152 mg Caffeine 32.4 mg PainAway: Add a spray of 5 mM Ammonium Bicarbonate at 1 μl/min Without liquid With liquid
Transcript of Shida Shen, Craig Whitehouse and Avinash Dalmia
PerkinElmer, Inc., 940 Winter Street, Waltham, MA USA (800) 762-4000 or (+1) 203 925-4602 www.perkinelmer.com
Introduction 1
The enclosed DSA ion source was mounted to a PerkinElmer AxION 2 TOF mass spectrometer (MS). The integral multiple inlet reagent ion generator position was adjustable relative to the sampling and MS entrance. Reagent ion gas composition, flow rate and temperature, countercurrent heated gas flow rate and temperature, and purge gas flow rate were adjustable through software controls. Solid and liquid samples were introduced into the ion source individually or in batches. They were mounted on a four axis translator with sample position controlled through software. For all samples, nitrogen was used as the carrier gas. For samples with low proton affinity, different reagent ions were added as gas or nebulized and vaporized liquid to improve sample ionization efficiency. The reagent ion generator was operated in APCI mode as well for direct ionization of liquid and gas samples calibration solution. The sample target position was controlled using a four axis translator stage with three linear axis and one rotating axis. Different sample types were mounted on round or square sample holders . The reagent ion generator was mounted on a three axis translator to allow optimization of the exit position. Sample was heated through the heated gas delivered from the reagent ion generator . Gas temperature and flow rate was adjusted maximize signal.
Performance of an Enclosed Atmospheric Pressure Direct Sample Analysis (DSA) Source Shida Shen, Craig Whitehouse and Avinash Dalmia
A novel enclosed Direct Sample Analysis (DSA) ion source was developed for the direct analysis of solid, liquid and gas samples using Atmospheric Pressure Chemical Ionization and Electrospray charged droplet charge transfer. The enclosed ion source allows programmed control of the reagent ion population, carrier gas species, enthalpy transfer and voltages in ionization and sampling region. Gas entering the ion source during operation can be vented to an exhaust system to avoid exposing the user to vaporized sample. Voltages are applied to the sampling inlet electrodes without exposure to the user during operation. Improved ionization and sampling efficiencies result from a combination of optimized heated gas flow and electric fields in the source and ion transport regions.
Experiments 3
Method 2
41.02 42.02 66.02 98.11
102.14
103.15 124.06 152.16 178.78 206.20 232.95 260.30 287.23 314.29 341.38 369.34 396.61
0
500000
1000000
1500000
2000000
2500000
3000000
3500000
0 50 100 150 200 250 300 350 400 450
MassRET (255.67808)
Amplitude
m/z
Curve 1
40.02 40.55 70.07
74.11
94.26 117.07 144.16 171.14 197.85 225.12 252.20 280.28 308.29 336.39 364.38 391.32 0
500000
1000000
1500000
2000000
2500000
3000000
3500000
0 50 100 150 200 250 300 350 400 450
MassRET (07.38783)
Amplitude
m/z
Curve 1
Diethylamine
Triethylamine
40.03
45.04
55.53 72.09 87.02
97.09 123.11 147.11
157.82
163.14
164.15
175.93 194.12 212.15 230.05 248.17 266.20 284.21 0
250000
500000
750000
1000000
1250000
1500000
1750000
2000000
50 100 150 200 250 300
MassRET (09.72716)
Amplitude
m/z
Curve 1Nicotine
Gas Samples
Cigarette Smoke
Experiments 3 Solid Samples
40.01 40.53 64.96 90.05
121.01
122.02 139.02
152.05
163.02
190.06
195.07
196.07 234.76 241.03
265.11 297.11 355.05 361.07
411.20 441.08 473.20 0
500000
1000000
1500000
2000000
2500000
50 100 150 200 250 300 350 400 450 500
MassRET (69.57083)
Amplitude
m/z
Curve 1
Caffeine
Acetaminophen
Fragment of Aspirin
M-H2O of Aspirin
PainAway Tablet
40.01
43.00 45.02
53.00 78.05 115.02
121.02
121.07 122.02
149.01
150.01
157.03
163.02
197.07
198.06
203.08
227.06
277.11
278.11 308.11 339.10
361.07
369.13 399.11 429.13 459.15 0
500000
1000000
1500000
2000000
2500000
50 100 150 200 250 300 350 400 450 500
MassRET (03.33833)
Amplitude
m/z
Curve 1
M-H2O of Aspirin
Fragment of Aspirin Baby Aspirin Tablet
Powder Samples
286.15 300.12 301.21
302.22 309.11 309.20 316.20 323.12
337.25
338.25 339.01
339.12
339.25 345.27 352.28 359.26
369.13
370.13
371.13
371.31
372.09 372.32
379.27 387.23 0
2500
5000
7500
10000
12500
15000
290 300 310 320 330 340 350 360 370 380 390 400
MassRET (02.49816)
Amplitude
m/z
Curve 1
Bisdemethoxy Curcumin
Demethoxy Curcumin
Curcumin (MH+=369.13325) Turmeric Powder
43.98 56.01
59.05
63.04 91.05 138.01 195.10 252.16
271.20
289.21
290.21
311.18 368.24 424.86 485.29 549.59
577.41
578.42
579.42
606.39 666.46 724.59 780.79 852.74 913.59 0
50000
100000
150000
200000
250000
300000
350000
400000
0 100 200 300 400 500 600 700 800 900 1000
MassRET (00.88150)
Amplitude
m/z
Curve 1
Testosterone [M+H]+ Dimer [2M+H]+
Testosterone Powder
107.04 116.05
135.07
141.10 170.08 175.10
195.08
199.06
220.27 263.23 268.13
269.14
270.14
288.17 313.15 338.14 366.35 371.30
391.24 440.32 465.12 0
50000
100000
150000
200000
250000
300000
100 150 200 250 300 350 400 450 500
MassRET (00.83816)
Amplitude
m/z
Curve 1
Diethyl Stilbestrol [M+H]+
Diethyl Stilbestrol
Experiments 3 Liquid Samples
Liquid Samples Are Dispensed onto a Mesh Target Prior to Running in the DSA Source.
45.03 51.02 78.98 112.04 151.11 209.02
216.10
217.10
218.10
248.04 287.16 329.18 371.10 410.22 450.20 490.02 530.21 570.27 609.38 0
50000
100000
150000
200000
250000
300000
350000
400000
450000
100 200 300 400 500 600 700
MassGEN (04.32583:04.33583)
Amplitude
m/z
Curve 1
42.03
43.02
45.03
51.02
56.01
57.02
59.05
81.07 114.05
149.02
153.09
216.09
217.09
218.09
219.09
256.25
277.15 280.25
282.27
284.29
338.33 340.34 379.27 418.37 457.29 496.18 535.50 574.41 613.52 654.15
0
5000
10000
15000
20000
25000
30000
35000
100 200 300 400 500 600 700
MassRET (04.17116)
Amplitude
m/z
Curve 1
100.07
114.09
136.02
149.03
151.07
172.13 211.09
216.10
218.10
256.27
279.17 280.27
282.28
284.30
290.97 365.18 369.36
371.11
400.26 438.46 476.38 518.30 553.54 591.60 638.64 674.63 0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
5500
6000
6500
100 150 200 250 300 350 400 450 500 550 600 650 700
MassRET (00.48783)
Amplitude
m/z
Curve 1
199.17
200.17
201.02
201.18
202.18
203.06 203.09
205.09
207.05 207.16
208.14
209.11 211.13
211.16
213.09
213.16
214.18
215.19
216.10
216.19
217.18
218.10
219.06 219.11
221.15
223.08
223.15 225.14
227.10 227.20
228.20
229.07
229.21
231.11
0
100
200
300
400
500
600
700
800
900
200 205 210 215 220 225 230
MassRET (01.70800)
Amplitude
m/z
Curve 1
1000 ppb
10 ppb
100 ppb
3 ppb
Atrazine in Tap Water
41.03
56.01 69.03
81.03
85.02
96.04
115.03 125.06
127.03
143.03
145.04
163.05
163.13
180.08
183.08 197.10
198.09
200.10
202.04
203.13 231.99 272.13
306.11
325.11
342.13
343.13
346.16 375.16
378.15
404.16 434.18 487.16
0
5000
10000
15000
20000
25000
30000
50 100 150 200 250 300 350 400 450 500
MassRET (05.00800)
Amplitude
m/z
Curve 1
Thiabendazole [M+H]+
1 ppm Thiabendazole spiked in apple juice
153.1287
283.2641
357.2999
397.3827
411.3984
575.5016
577.5180
601.5172
603.5331
605.5430 859.7679
0
5000
10000
15000
20000
25000
30000
35000
40000
0 100 200 300 400 500 600 700 800 900 1000
MassGEN (14.25600:14.75600)
Amplitude
m/z
Curve 1
[OO+H]+
[OP+H]+
[OS+H]+
[LP+H]+
Olive Oil Characterization
855.74 856.76
857.76
858.77
859.78
860.78
861.78
875.77 877.80
881.76
883.78
884.78
885.80
886.80
887.80
888.80 901.77 903.80
922.02
923.02
0
250
500
750
1000
1250
1500
1750
850 860 870 880 890 900 910 920
MassGEN (14.25600:14.75600)
Amplitude
m/z
Curve 1[OOO+H]+
[OLO+H]+
[OPO+H]+
[POL+H]+
Zoom in
40.02 66.00 87.00 134.05
151.11
191.06 253.20
255.23
279.22
281.24
282.24 310.25 377.11 433.34
537.47 551.97
563.49
564.49 637.52 694.55 751.57 808.56 864.91 921.69
0
25000
50000
75000
100000
125000
150000
0 100 200 300 400 500 600 700 800 900 1000
MassRET (02.47483)
Amplitudem/z
Curve 1
41.99
44.99
59.98
115.07 145.05
255.22
277.20
278.21
279.22
280.23
281.24
282.24 386.25
415.34 434.33
444.34
448.34
512.32 624.47
689.57 768.47 886.69 887.70
906.64 972.76 0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
5500
6000
0 100 200 300 400 500 600 700 800 900 1000
MassRET (05.82483)
Amplitude
m/z
Curve 1
41.00 73.03 97.02 151.99
255.23 277.21
279.23
280.23
281.25
282.25
301.23 389.28
448.35
455.18 551.33 561.48 563.49
564.49 618.46 684.53 750.12 815.75 886.63 952.58
0
5000
10000
15000
20000
25000
30000
35000
40000
45000
0 100 200 300 400 500 600 700 800 900 1000 1100
MassRET (96.13183)
Amplitude
m/z
Curve 1
Olive Oil
Vegetable Oil
Canola Oil
Oleic
Oleic
Oleic
Palmitic
Palmitic
Palmitic Linoleic
Linoleic
Linoleic
Linolenic
Linolenic
Palmitoleic
Cooking Oil
Other Applications 4
0
2500
5000
7500
10000
12500
15000
17500
20000
22500
304.125
304.150
304.175
304.200
304.225
304.250
304.275
304.300
16.5 17.0 17.5 18.0 18.5 19.0 19.5 20.0 20.5
BICm/z (303.959:304.345)
Amplitude
m/z
Time (min)
Amplitude
m/z
$20 bill $5 bill $1 bill $100 bill
“Hotness” of Peppers
251.18 268.20 276.17 292.81
304.16
308.23
309.22
324.08
326.25
339.27 364.24
367.27
382.29
384.30
385.30
398.31 419.32
425.32
436.34
442.34
443.35
452.30 480.37 483.36
500.38
0
1000
2000
3000
4000
5000
6000
7000
8000
9000
250 300 350 400 450 500
MassRET (18.07366)
Amplitude
m/z
Curve 1
242.28 258.11 274.16 290.14
304.15
305.16
323.15
326.25
339.20 354.91
384.30
388.15 391.29
394.22 404.20 420.19 439.23 442.34
455.25 471.20 487.36 0
5000
10000
15000
20000
25000
250 300 350 400 450 500
MassRET (18.77358)
Amplitude
m/z
Curve 1
Cocaine MH+=304.15432
Cocaine
19 times higher ! $20 bill
$5 bill
Trace Amount Cocaine on US Paper Currency
279.01 279.23
282.27
284.29 285.28 288.28 291.19 294.05 297.07 300.16 303.26
306.20
307.21
308.22
309.22 312.20 315.12 318.18 321.21 324.23
0
25000
50000
75000
100000
125000
150000
175000
200000
225000
280 285 290 295 300 305 310 315 320 325 330
MassRET (02.48483)
Amplitude
m/z
Curve 1
302.17 303.20 304.00 305.23 306.00
306.20
307.20
307.96
308.21
308.36 309.22
310.24 311.04 312.12 313.12 0
2500
5000
7500
10000
12500
15000
17500
20000
22500
302 303 304 305 306 307 308 309 310 311 312 313 314
MassRET (04.11816)
Amplitude
m/z
Curve 1
289.08
290.22
292.23 293.16 293.23
294.18
295.20 296.19
297.20
298.20 299.27 301.13
301.21
304.00
304.24
305.23
306.20
307.21
308.22
309.19 309.25
310.16
311.23
313.12 315.11
316.24 317.25
318.18 320.97
321.25 323.22
325.10
327.23
328.23 330.26
0
50
100
150
200
250
300
350
400
450
500
550
600
290 295 300 305 310 315 320 325 330
MassRET (03.71816)
Amplitude
m/z
Curve 1
Jalapeno Pepper
Chilli Pepper
Cubanelle Pepper
Dihydro apsaicin
Capsaicin
Dihydro Capsaicin
Dihydro Capsaicin
Capsaicin
Capsaicin
Melatonin in Lazy Cakes
95.04
97.02
109.02
111.04 126.05
127.03
139.03
145.04
152.07
163.05
180.08
181.06
182.07
193.04
195.08
206.08 219.07 231.92
233.12
245.10 258.10 271.07 284.06 0
10000
20000
30000
40000
50000
60000
70000
100 125 150 175 200 225 250 275 300
MassRET (00.47150)
Amplitude
m/z
Curve 1
Melatonin MH+ = 233.1285
Conclusion 5 The DSA ion source with automated sample positioning allows multiple samples to be loaded and run in a sealed enclosure. Ions have been generated from solid, liquid and gas samples in both positive and negative ion polarity mode. Powder samples were run in small amounts loaded onto a melting point tube. The reagent ion generator is configured with multiple gas and a liquid inlet. The liquid is nebulized and vaporized allowing tight control of reagent ion concentration, such as water. The reagent ion generator configured with an internal corona discharge needle near the exit end can also be operated as an APCI inlet probe to directly ionize gas and nebulized and vaporized liquid samples. Calibration solution for accurate mass TOF MS was introduced as a liquid into the ion generator. Voltages applied to the mass spectrometer capillary entrance electrodes improve ion sampling efficiency compared to ions sampled using gas flow alone. The sealed enclosure prevents the user from being exposed to the samples being run. The source enclosure is purged with nitrogen gas and vented to a laboratory exhaust system. In all studies reported here, nitrogen was used as the carrier gas yielding high ionization efficiency for most of the samples run. For samples with low proton affinities, adding a reagent species such as ammonia improved ionization efficiency.
Auxiliary Gas Inlet
Nebulization Gas Inlet Liquid Inlet Heater
N2 Corona
Needle
Sample
02 ccs 2009 11 04 ee_1
26024022020018016014012010080m/z
8
16
24
32
40
48
56
64
72
80
88
96
Rela
tive Inte
nsity (
%)
74
102
121
138
163
177
195
224
240
254
02 ccs 2009 11 04 ed_1
220210200190180170160150140130120110100908070m/z
8
16
24
32
40
48
56
64
72
80
88
96
Rela
tive Inte
nsity (
%)
73 87 110
121
138152
167
195
207227
Active ingredients (in each tablet) Acetaminophen 110 mg Aspirin 162 mg Salicylamide 152 mg Caffeine 32.4 mg
PainAway: Add a spray of 5 mM Ammonium Bicarbonate at 1 µl/min
Without liquid With liquid
