Ispitivanje reakcija hidrolize i kompleksiranja u rastvorima aluminijum(III)-jona i nekih fluorohinolona metodom elektrosprej-tandem masene spektrometije

Abstract

Predmet ove disertacije je proučavanje reakcija hidrolize aluminijum(III)-jona i reakcija kompleksiranja aluminijum(III)-jona i fluorohinolona (HQ) (fleroksacina, ciprofloksacina i moksifloksacina). U okviru disertacije određena je specijacija u rastvorima aluminijum(III)-jona i rastvorima aluminijum(III)-jona i fluorohinolona (HQ) sa ciljem boljeg razumevanja farmako i toksikokinetike fluorohinolonskih antibiotika u prisustvu lekova na bazi aluminijuma (antacidi, vakcine, dijalizatni rastvori). Proučavanja su vršena elektrosprej masenom spektrometrijom, (ESI MS), tandem masenom spektrometrijom (MS/MS) i masenom spektrometrijom, gde je jonizacija potpomognuta laserskom desorpcijom iz matriksa (MALDI MS). Proučavanjem navednih sistema, pomenutim eksperimentalnim tehnikama i kompjuterskom obradom podataka, korišćenjem programa Hyss 2006 i modela veštačkih neuronskih mreža (AAN) dobijeni su sledeći rezultati: Pri proučavanju hidrolize aluminijuma vrste identifikovane u rastvorima aluminijum(III)-jona, koncetracije 0,03 do 5,0 mmol/dm3, su vrste sa naelektrisanjem +1, +2 i +3, formirane u opsegu pH od 3-6. Monomerne i dimerne vrste su dominantne do pH 3,8. ESI MS spektri ukazuju na formiranje malih polimernih vrsta (Al3–Al5) na pH 4,8. Sa povećanjem pH i koncetracije aluminijum(III)-jona identifikuju se srednji polimeri (Al6–Al10). Daljim povećanjem pH i koncentracije aluminijum(III)-jona nastaju viši polimeri (Al11–Al13). Viši polimeri su privremene vrste koje postoje relativno kratko vreme nakon pripreme rastvora. Na pH oko 6,4 počinje formiranje taloga. Rezultati dobijeni ESI masenom spektrometrijom su u saglasnosti sa rezultatima dobijenim 27 Al NMR spektroskopijom i potenciometrijom.

Th is dissertation comprises investigation of hydrolysis aluminum(III)-ion and aluminum(III)-ion and fl uoroquinolones (FQLs) family members (fl eroxacin, ciprofl oxacin and moxifl oxacin) complexation reactions. Within present study it is determined speciation in solutions of aluminum(III)-ion and in solutions of aluminum(III)-ions and fl uoroquinolones (FQLs) in aim to better understand pharmacotherapy and toxicokinetics of fl uoroquinolones antibiotics in the presence of aluminum-based drugs (antacids, vaccines, solutions for dialysis). So the solutions were investigated by electrospray mass spectrometry (ESI MS), tandem mass spectrometry (MS/MS) and mass spectrometry with matrix-assisted laser desorption ionization (MALDI MS). Investigation or these systems, using the above mentioned experimental techniques and computer processing data by using Hyss 2006 soft ware and artifi cial neural network (AAN) model gave the following results: Th e hydrolysis of aluminum(III)-ion have been investigated in the solutions of concentration level 0,03 to 5,0 mmol/dm3, in the pH range 3 to 6. Th e species with electric charge +1, +2 and +3, formed in this conditions. Monomeric and dimeric species were dominant until the pH value of 3,8. ESI MS spectra indicate the formation of small polymeric species (Al3-Al5) at pH 4,8 value. With the increase pH and concentrations values of aluminum(III)-ion, it was identifi ed intermediate polymers (Al6-Al10). With further increase in pH and the concentration of aluminum(III)-ion, higher polymers (Al11-Al13) were generated. Higher polymers are species that are relatively short period of time existing. At a pH of about 6,4 the sludge formed. Th e results obtained by ESI MS spectra are in good agreement with the results obtained by 27Al NMR spectroscopy and by potentiometry.