title: Estimation of lead in biological samples of oral cancer patients chewing smokeless tobacco products by ionic liquid-based microextraction in a single syringe system.
abstract: Several studies have reported that the chewing habit of smokeless tobacco (SLT) has been associated with oral cancer. The aim of the present study was to evaluate the trace levels of lead (Pb) in biological samples (blood, scalp hair) of oral cancer patients and referents of the same age group (range 30-60 years). As the concentrations of Pb are very low in biological samples, so a simple and efficient ionic liquid-based microextraction in a single syringe system has been developed, as a prior step to determination by flame atomic absorption spectrometry. In this procedure, the hydrophobic chelates of Pb with ammonium pyrrolidinedithiocarbamate (APDC) were extracted into fine droplets of 1-butyl-3-methylimidazolium hexafluorophosphate [C4MIM][PF6] within a syringe while using Triton X-114 as a dispersant. Factors influencing the microextraction efficiency and determination, such as pH of the sample, volume of [C4MIM][PF6] and Triton X-114, ligand concentration, and incubation time, were studied. To validate the proposed method, certified reference materials were analyzed and the results of Pb(2+) were in good agreement with certified values. At optimum experimental values of significant variables, detection limit and enhancement factor were found to be 0.412 μg/L and 80, respectively. The coexisting ions showed no obvious negative outcome on Pb preconcentration. The proposed method was applied satisfactorily for the preconcentration of Pb(2+) in acid-digested SLT and biological samples of the study population. It was observed that oral cancer patients who consumed different SLT products have 2-3-fold higher levels of Pb in scalp hair and blood samples as compared to healthy referents (p < 0.001). While 31.4-50.8% higher levels of Pb were observed in referents chewing different SLT products as compared to nonconsumers (p < 0.01).
authors.affiliation: National Center of Excellence in Analytical Chemistry, University of Sindh, Jamshoro, 76080, Pakistan, ssadiashafi@gmail.com.
authors.forename: Sadaf S
authors.initials: SS
authors.lastname: Arain
authors.forename: Tasneem G
authors.initials: TG
authors.lastname: Kazi
authors.forename: Asma J
authors.initials: AJ
authors.lastname: Arain
authors.forename: Hassan I
authors.initials: HI
authors.lastname: Afridi
authors.forename: Muhammad B
authors.initials: MB
authors.lastname: Arain
authors.forename: Kapil D
authors.initials: KD
authors.lastname: Brahman
authors.lastname: Naeemullah
authors.forename: Abdul H
authors.initials: AH
authors.lastname: Panhwar
authors.forename: Mariam S
authors.initials: MS
authors.lastname: Arain
mesh_terms: D000328:Adult; D002614:Chelating Agents / Q000737:chemistry; D005260:Female; D006197:Hair / Q000737:chemistry*; D006801:Humans; D007093:Imidazoles / Q000737:chemistry; D052578:Ionic Liquids / Q000737:chemistry*; D007854:Lead / Q000097:blood* / Q000737:chemistry / Q000302:isolation & purification*; D008024:Ligands; D057230:Limit of Detection; D059627:Liquid Phase Microextraction / Q000295:instrumentation / Q000379:methods*; D008297:Male; D008875:Middle Aged; D009062:Mouth Neoplasms / Q000097:blood*; D011759:Pyrrolidines / Q000737:chemistry; D012044:Regression Analysis; D013054:Spectrophotometry, Atomic; D013594:Syringes; D013859:Thiocarbamates / Q000737:chemistry; D014030:Tobacco, Smokeless / Q000009:adverse effects*
chemical_list: C412621:1-butyl-3-methylimidazolium hexafluorophosphate; D002614:Chelating Agents; D007093:Imidazoles; D052578:Ionic Liquids; D008024:Ligands; D011759:Pyrrolidines; D013859:Thiocarbamates; C020972:pyrrolidine dithiocarbamic acid; D007854:Lead