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

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Page 1: 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