Study on the Mass Spectrometry Fragmentation Patterns for Rapid Screening and Structure Identification of Ketamine Analogues in Illicit Powders
Abstract
:1. Introduction
2. Results and Discussion
2.1. Overview of the Common Structure, EI-MS and ESI-MS/MS Fragmentation Patterns of Ketamine Analogues
2.2. Mass Spectra Results of Ketamine Analogues Reference Substances
2.3. Structure Elucidation of Ketamine Analogues Reference Substances
2.3.1. 2-phenyl-2-(methylamino)cyclohexanone (DCK) and 2-(Ethylamino)-2-phenylcyclohexan-1-one (2-oxo-PCE)
2.3.2. 2-(3-methoxyphenyl)-2-(ethylamino)cyclohexanone (MXE)
2.3.3. 2-(2-Chlorophenyl)-2-(methylamino)cyclohexanone (Ketamine), 2-(2-Fluorophenyl)-2-(methylamino) cyclohexan-1-one (F-Ketamine), 2-(2-Bromophenyl)-2-(methylamino) cyclohexan-1-one (Br-Ketamine) and 2-(2-Chlorophenyl)-2-(ethylamino) cyclohexanone (NENK)
2.3.4. 2-(Ethylamino)-2-(m-tolyl)cyclohexan-1-one (DMXE)
2.4. Analysis of Mass Spectrometry Fragmentation Patterns of Ketamine Analogues
3. Qualitative Analysis of Suspicious Powder
4. Materials and Methods
4.1. Materials
4.2. Instrument
4.2.1. GC-Q-TOF/MS Analysis
4.2.2. LC-Q-Orbitrap/MS Analysis
4.3. Sample Preparation
5. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
Sample Availability
References
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No. | Compound Structures | Formula | Accurate m/z ([M+]) | Theoretical m/z ([M+]) | Accurate m/z ([M + H]+) | Theoretical m/z ([M + H]+) | RSD (ppm) a |
---|---|---|---|---|---|---|---|
1 | DCK: | C13H17NO | 203.1302 | 203.1310 | 204.13843 | 204.13829 | −3.94/0.69 |
2 | 2-oxo-PCE: | C14H19NO | 217.1463 | 217.14666 | 218.15404 | 218.15394 | −1.65/0.46 |
3 | MXE: | C15H21NO2 | 247.1567 | 247.15723 | 248.16451 | 248.16451 | −2.14/0 |
4 | Ketamine: | C13H16ClNO | 237.0913 | 237.09204 | 238.09952 | 238.09932 | −3.12/0.84 |
5 | F-Ketamine: | C13H16FNO | 221.1205 | 221.12159 | 222.12936 | 222.12887 | −4.93/2.20 |
6 | Br-Ketamine: | C13H16BrNO | 281.0423 | 281.04153 | 282.04880 | 282.04880 | 2.73/0 |
7 | NENK: | C14H18ClNO | 251.1072 | 251.10769 | 252.11505 | 252.11497 | −1.95/0.32 |
8 | DMXE: | C15H21NO | 231.1617 | 231.16231 | 232.16963 | 232.16959 | −2.64/0.17 |
Comp. | Molecular Ion (m/z) | Fragmentation Ions (m/z) |
EI-MS | ||
1 | 203.1302 | 175.1358 (Path 1, 2), 160.1127 (Path 3), 146.1042 (Path 5), 132.0811 (Path 4, 7), 117.0699 (Path 6), 104.0500 (Path 7), 91.0546 (Path 8), 77.0389 (Path 8) |
2 | 217.1463 | 189.1518 (Path 1, 2), 174.1283 (Path 3), 160.1144 (Path 5), 146.0970 (Path 4), 132.0813 (Path 7), 117.0701 (Path 6), 104.0500 (Path 7), 91.0546 (Path 8), 77.0389 (Path 8) |
3 | 247.1567 | 219.1619 (Path 1, 2), 204.1387 (Path 3), 190.1301 (Path 5), 176.1085 (Path 4), 162.0915 (Path 7), 147.0805 (Path 6), 134.0603 (Path 7), 121.0650 (Path 8),91.0539 (Path 8), 77.0388 (Path 8) |
4 | 237.0913 | 209.0965 (Path 1, 2), 194.0732 (Path 3), 180.0591 (Path 5), 166.0418 (Path 7), 145.0885 (Path 1) 138.0105 (Path 7), 125.0151 (Path 8), 115.0542 (Path 6), 102.0341 (Path 7), 75.0229 (Path 8) |
5 | 221.1205 | 193.1265 (Path 1, 2), 178.1034 (Path 3), 164.0942 (Path 5), 150.0718 (Path 4, 7), 135.0606 (Path 6), 122.0406 (Path 7), 115.0547 (Path 6), 109.0542 (Path 8), 102.0345 (Path 7), 75.0232 (Path 8) |
6 | 281.0423 | 253.0480 (Path 1, 2), 238.0219 (Path 3), 224.0092 (Path 5), 209.9915 (Path 4, 7), 194.9801 (Path 6), 181.9616 (Path 7), 168.9652 (Path 8), 145.0900 (Path 1), 115.0553 (Path 6), 102.0470 (Path 7), 75.0229 (Path 8) |
7 | 251.1072 | 223.1125 (Path 1, 2), 208.0890 (Path 3), 194.0758 (Path 5), 180.0579 (Path 4), 166.0423 (Path 7), 151.0312 (Path 6), 138.0108 (Path 7), 125.0156 (Path 8), 115.0545, 102.0342 (Path 8), 75.0232 (Path 8) |
8 | 231.1617 | 203.1669 (Path 1, 2), 188.1438 (Path 3), 174.1284 (Path 5), 160.1124 (Path 4), 146.0967 (Path 7), 131.0855 (Path 6), 118.0654 (Path 7), 105.0701 (Path 8), 91.0544 (Path 8), 77.0387 (Path 8) |
Comp. | Precursor Ion (m/z) | Fragmentation Ions (m/z) |
ESI-MS/MS | ||
1 | 204.13843 | 186.12746 (Path 10), 173.09630 (Path 9), 145.10135 (Path 9), 91.05433 (Path 9) |
2 | 218.15404 | 200.14333 (Path 10), 173.09624 (Path 9), 145.10124 (Path 9), 91.05428 (Path 9) |
3 | 248.16451 | 230.15408 (Path 10), 203.10672 (Path 9), 175.11182 (Path 9), 121.06484 (Path 9) |
4 | 238.09952 | 220.08894 (Path 10), 207.05742 (Path 9), 179.06247 (Path 9), 125.01547 (Path 9), 163.03113 |
5 | 222.12936 | 204.11887 (Path 10), 191.08719 (Path 9), 163.09216 (Path 9), 109.04510 (Path 9) |
6 | 282.04880 | 264.03821 (Path 10), 251.00664 (Path 9), 223.01180 (Path 9), 168.96486 (Path 9), 172.08832 |
7 | 252.11505 | 234.10452 (Path 10), 207.05725 (Path 9), 179.06230 (Path 9), 125.01538 (Path 9), 163.03096 |
8 | 232.16963 | 214.15903 (Path 10), 187.11192 (Path 9), 159.11699 (Path 9), 105.07034 (Path 9) |
EI-QTOF/MS | ||||
---|---|---|---|---|
Compound | Chemical Formula | Exact Mass | Accurate Mass | Error (ppm) |
1 | C14H19NO+ | 217.1461 | 217.1461 | 0.0 |
C13H19N+ | 189.1512 | 189.1515 | 1.6 | |
C12H16N+ | 174.1277 | 174.1282 | 2.9 | |
C11H14N+ | 160.1121 | 160.1125 | 2.5 | |
C10H12N+ | 146.0964 | 146.0967 | 2.1 | |
C9H10N+ | 132.0808 | 132.0814 | 4.5 | |
C10H11+ | 131.0855 | 131.0849 | −4.6 | |
C8H9+ | 105.0699 | 105.0702 | 2.9 | |
C7H7+ | 91.0542 | 91.0546 | 4.4 | |
C6H5+ | 77.0386 | 77.0389 | 3.9 | |
ESI-Q-Orbitrap MS/MS | ||||
1 | C14H20NO+ | 218.15394 | 218.15405 | 0.5 |
C14H18N+ | 200.14338 | 200.14354 | 0.8 | |
C13H15O+ | 187.11174 | 187.11191 | 0.9 | |
C12H15+ | 159.11683 | 159.11697 | 0.9 | |
C8H9+ | 105.06988 | 105.06996 | 4.7 |
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Fan, Y.; Gao, J.; Chen, X.; Wu, H.; Ke, X.; Xu, Y. Study on the Mass Spectrometry Fragmentation Patterns for Rapid Screening and Structure Identification of Ketamine Analogues in Illicit Powders. Molecules 2023, 28, 6510. https://doi.org/10.3390/molecules28186510
Fan Y, Gao J, Chen X, Wu H, Ke X, Xu Y. Study on the Mass Spectrometry Fragmentation Patterns for Rapid Screening and Structure Identification of Ketamine Analogues in Illicit Powders. Molecules. 2023; 28(18):6510. https://doi.org/10.3390/molecules28186510
Chicago/Turabian StyleFan, Yilei, Jianhong Gao, Xianxin Chen, Hao Wu, Xing Ke, and Yu Xu. 2023. "Study on the Mass Spectrometry Fragmentation Patterns for Rapid Screening and Structure Identification of Ketamine Analogues in Illicit Powders" Molecules 28, no. 18: 6510. https://doi.org/10.3390/molecules28186510