Potential Doping Substances Detected in Boosters in Poland
Kwiatkowska, D1), Pokrywka, A1), Jarek, A1), Gorczyca, D 1)
Potential doping substances detected in boosters in Poland
1)Department of Anti-Doping Research, Institute of Sport, Warsaw, Poland
Abstract
In 2003 the World Anti-Doping Agency (WADA) took responsibility for the List of substances and methods prohibited in sport (the Prohibited List). Since that moment the list has been regularly updated, and all changes, based mainly on scientific research, have been preceded by numerous consultations with representatives of the sport and medicine. By publishing a new version of the Prohibited List every year and by enlisting numerous examples of prohibited substances WADA fulfilled partly the need of publishing a complete list of prohibited substances. However, the Prohibited List still has an open character. In spite of the examples of prohibited substances or methods in particular groups, some additional substances, which are not located on the list but are characterized by “a similar chemical structure or similar biological effect(s)”, can be considered as doping.
Introduction
In recent years several well-known Polish athletes have personally found out what this definition means. In their urine samples 4-methyl-2-hexaneamine and beta- methylphenylethylamine were detected during the doping control. These substances, which were found also in dietary supplements, were not mentioned on the WADA Prohibited List at the time. However, both substances were recognized by WADA as banned in sport because of chemical similarity to the structure of tuaminoheptane and amphetamine. Potential doping substances can be also ingredients of boosters (legal highs, smarts, party pills). This work presents the results of analyses of several products from Polish market
Materials and Methods
The laboratory analysed 50 boosters available on the polish market. Samples were analysis by GC-MS in a SCAN mode (GC5890 – MS5975N, Agilent Technologies). GC program: 65°C
WS2011 – POSTER 266 (2,00 min); 250 °C (15 °C/min, 6,00 min); 300 °C (20 °C/min, 4,00 min): Column: HP-5MS, 0.25 mm, ID 0.25 mm, 12 m. Injection volume 1 µL, Splitless. Standards were purchased from LGC Standards (Poland).
Results and Discussion
During the analysis laboratory found substances as follow (in alphabetical order):
butylone (bk-MBDB; 1-(1,3-benzodioxol-5-yl)-2-(methylamino)butan-1-one) caffeine; (1,3,7-trimethyl-1H-purine-2,6(3H,7H)-dione) DBZP (dibenzylpiperazine;1,4-dibenzylpiperazine) ephedrine artefact (3,4-dimethyl-5-phenyl-1,3-oxazolidine) ethylone (1-(1,3-benzodioxol-5-yl)-2-(ethylamino)propan-1-one) JWH-081 (4-methoxynaphthalen- 1-yl- (1-pentylindol- 3-yl)methanone) MBZP (methylbenzylpiperazine;1-methyl-4-(phenylmethyl)piperazine;1-methyl-4- benzylpiperazine;1-benzyl-4-methylpiperazine) MDPV (methylenedioxypyrovalerone;1-(benzo[d][1,3]dioxol-5-yl)-2-(pyrrolidin-1-yl) pentan-1-one) 4-MEC (4-methyl-N-ethylcathinone) metamfepramone (2-(dimethylamino)-1-phenylpropan-1-one) methedrone (bk-PMMA;1-(4-methoxyphenyl)-2-(methylamino)propan-1-one) methylone (bk-MDMA; (±)-2-methylamino-1-(3,4-methylenedioxyphenyl)propan-1-one) lidocaine (2-(diethylamino)-N-(2,6-dimethylphenyl)acetamide) pFPP (para-Fluorophenylpiperazine1-(4-fluorophenyl)piperazine) 3-Phenyl-1H-pyrazole (5-phenyl-1H-pyrazole) pentylone (bk-MBDP; (±)-1-(1,3-benzodioxol-5-yl)-2-(methylamino)pentan-1-one) TFMPP (trifluoromethylphenylpiperazine;1-[3-(trifluoromethyl) phenyl]piperazine)
All substances detected by the Warsaw Anti-Doping Laboratory may by reported as potential doping substances. The following substances for which the structure and MS spectrum is shown match the definition of doping substances due to their chemical similarity to items mentioned in the PROHIBITED LIST. Many other compounds found also could be doping substances eg methcathinone derivatives etc..
WS2011 – POSTER 267 1) class S6 STIMULANTS - DBZP (dibenzylpiperazine;1,4-dibenzylpiperazine)
Abundance
Scan 1876 (13.021 min): al10-3278.D\data.ms (-) 55000 91.0 50000
45000
40000 N 35000 30000 N 25000 20000
15000 120.1 175.1 10000 65.0 266.1 5000 146.0 42.0 194.0 238.1 298.1 0 40 60 80 100 120 140 160 180 200 220 240 260 280 300 m/z-->
- pFPP (para-Fluorophenylpiperazine1-(4-fluorophenyl)piperazine)
Abundance
Scan 760 (7.425 min): d10-3232.D\ data.ms (-675) (-) 138.1 8000
7500
7000
6500
6000 NH 5500 5000 N 4500 4000
3500
3000 180.1 2500
2000
F 1500
1000 95.2 500 223.2 354.8 430.8 63.3 269.1 318.2 463.2 0 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460 m/ z-->
- MBZP (methylbenzylpiperazine;1-methyl-4-(phenylmethyl)piperazine;1-methyl-4- benzylpiperazine;1-benzyl-4-methylpiperazine)
Abundance
Scan 1038 (8.137 min): al10-3274.D\data.ms (-) 91.1 1000000
900000
800000 N 700000 600000
190.1 N 500000
119.1 400000 56.1
300000
200000 146.1
100000
220.7 282.9 327.0 415.8 0 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 m/z-->
WS2011 – POSTER 268 - TFMPP (trifluoromethylphenylpiperazine;1-[3-(trifluoromethyl) phenyl]piperazine)
Abundance
Scan 1348 (9.944 min): al10-3232.D\ data.ms (-) 188.0 17000
16000
15000
14000 NH 13000 12000
11000 F C N 10000 3 9000 8000
7000
6000
5000 168.9 4000 230.2 3000 144.9 2000 56.0 83.5 211.0 1000 41.1 127.0 100.0 0 40 60 80 100 120 140 160 180 200 220 240 m/ z-->
- MDPV (methylenedioxypyrovalerone;1-(benzo[d][1,3]dioxol-5-yl)-2-(pyrrolidin-1- yl) pentan-1-one)
Abundance
Scan 1859 (12.922 min): al10-3239.D\data.ms (-1867) (-) 126.1 8000000
7000000
O 6000000
O N 5000000
4000000
O 3000000
2000000
1000000 65.0 42.1 96.0 149.0 176.9 204.1 232.1 256.0 274.1 0 40 60 80 100 120 140 160 180 200 220 240 260 280 m/ z-->
2) class S8 CANNABINOIDS - JWH-081 (4-methoxynaphthalen- 1-yl- (1-pentylindol- 3-yl)methanone)
Abundance
Scan 3976 (25.262 min): al10-3244.D\ data.ms (-) 3500000 371.2
3000000
2500000
2000000 314.1
N 1500000 214.1
185.1 1000000 144.0
43.1 114.1 500000 285.1 254.1 77.0 405.0 450.9 0 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 m/z-->
References 1. Perrenoud L, Saugy M, Saudan C. (2009) Detection in urine of 4-methyl-2-hexaneamine, a doping agent. J Chromatogr B, 877, 3767-3770.
WS2011 – POSTER 269