Approach to Optimization of Mass Spectrometric Detection Parameters for Identification of Ultra-Small Amounts of Highly Toxic Substances

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Resumo

The procedure of optimization of the following parameters is described: scanning speed, duration of registration of selective transitions (dwell time), duration of delay in transition from one selective transition to another (pause time). A chromatograph for HPLC with a three-quadrupole mass spectrometric detector (LC-MS/MS Shimadzu 8050) was used. Chromatographic separation was carried out on a column with reversed-phase sorbent Phenomenex Kinetex C18. As mobile phase A was used 0.1 % solution of formic acid in water with addition of 10 mM/L ammonium formate, as mobile phase B – 0.1 % solution of formic acid in methanol with addition of 10 mmol/L ammonium formate. The optimal parameters for confirmatory methods were established: duration of registration of selective transitions – not less than 10 ms, duration of delay in transition from one selective transition to another – 1 ms, scanning speed – from 1000 to 5000 scans per second. This technique has been successfully applied in routine chemical and toxicological studies of urine samples with low content of various narcotic and medicinal substances.

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Sobre autores

M. Aigumov

Noyabrsk Psychoneurological Dispensary

Autor responsável pela correspondência
Email: aygumov.m@yandex.ru
Rússia, Noyabrsk

S. Savchuk

Association of Specialists in Chemical-toxicological and Forensic Chemical Analysis; The Institute of Physical Chemistry and Electrochemistry RAS (IPCE RAS)

Email: aygumov.m@yandex.ru
Rússia, St. Petersburg; Moscow

Bibliografia

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  6. LC/MS/MS Forensic Toxicology DB, Instruction Manual, 225-28669A, April 2018.
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2. Fig. 1. Chromatographic profile of the PT-36 urine sample.

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3. Fig. 2. The mass spectrum of α-pyrrolidinovalerophenone at an impact energy of 30 eV.

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4. Fig. 3. Chromatographic profile of the PT-36 urine sample in 1/4000 dilution. The method is screening, with more than 300 detectable substances. The mass spectrum is unidentifiable, the coincidence with the library mass spectrum of α-pyrrolidinovalerophenone is less than 30%.

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5. Fig. 4. The results obtained by optimizing the delay duration during the transition from one selective transition to another, (a) the set value is 1 ms, (b) the set value is 5 ms, (c) the set value is 10 ms.

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6. Fig. 5. The results obtained by optimizing the duration of selective transition registration, (a) the set value is 0.8 ms, (b) the set value is 5 ms, (c) the set value is 10 ms.

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7. Fig. 6. The results obtained by optimizing the scanning speed, (a) the set value is 40 Da/s, the coincidence of the obtained mass spectrum with the library mass spectrum is 51%, (b) the set value is 1000 Da/s, the coincidence of the obtained mass spectrum with the library mass spectrum is 70%, (c) the set value is 30,000 Da/s, the coincidence of the obtained mass spectrum with the library mass spectrum is 54%.

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8. Fig. 7. (a) Chromatographic profile of the PT-36 urine sample in 1/4000 dilution, obtained by an optimized confirmatory method, matching the library mass spectrum of α-pyrrolidinovalerophenone 61%, (b) the mass spectrum of α-pyrrolidinovalerophenone at an impact energy of 30 eV.

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9. Fig. 8. Chromatographic profiles and mass spectra of a urine sample obtained by (a) screening and (b) confirmatory methods. The settings of the screening method are: the duration of registration of a selective transition is 2 ms, the delay time during the transition from one selective transition to another is 1 ms, and the scanning speed is 30,000 scans per second. The coincidence with the library mass spectrum is 35%. Confirmation method settings: the duration of registration of a selective transition is 10 ms, the delay time during the transition from one selective transition to another is 1 ms, and the scanning speed is 5,000 scans per second. The coincidence with the library mass spectrum is 86%.

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10. Fig. 9. Chromatographic profiles and mass spectra of a urine sample obtained by (a) screening and (b) confirmatory methods. The settings of the screening method are: the duration of registration of a selective transition is 2 ms, the delay time during the transition from one selective transition to another is 1 ms, and the scanning speed is 30,000 scans per second. The coincidence with the library mass spectrum is 33%. Confirmation method settings: the duration of registration of a selective transition is 10 ms, the delay time during the transition from one selective transition to another is 1 ms, and the scanning speed is 5,000 scans per second. The coincidence with the library mass spectrum is 88%.

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11. Fig. 10. Chromatographic profiles and mass spectra of a urine sample obtained by (a) screening and (b) confirmatory methods. The settings of the screening method are: the duration of registration of a selective transition is 2 ms, the delay time during the transition from one selective transition to another is 1 ms, and the scanning speed is 30,000 scans per second. The coincidence with the library mass spectrum is 34%. Confirmation method settings: the duration of registration of a selective transition is 10 ms, the delay time during the transition from one selective transition to another is 1 ms, and the scanning speed is 5,000 scans per second. The coincidence with the library mass spectrum is 91%.

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