title: Ultratrace analysis of uracil and 5-fluorouracil by molecularly imprinted polymer brushes grafted to silylated solid-phase microextraction fiber in combination with complementary molecularly imprinted polymer-based sensor.
abstract: Main inborn errors of metabolism diagnosable through uracil (Ura) analysis and the therapeutic monitoring of toxic 5-fluorouracil (5FU) in dihydro pyrimidine dehydrogenase (DPD) deficient patients require a sensitive, reproducible, selective and accurate method. In this work, an artificial receptor in the format of molecularly imprinted polymer (MIP) brush 'grafted to' the surface of sol-gel immobilized on cost-effective homemade solid-phase microextraction (SPME) fibers, individually imprinted with either of Ura and 5FU, was used in combination with a voltammetric sensor duly modified with the same MIP. This combination provided up to 10- and 8.4-fold preconcentrations of Ura and 5FU, respectively, which was more than sufficient for achieving stringent detection limits in the primitive diagnosis of uracil disorders and fluoropyrimidine toxicity in DPD-deficient patients. The proposed method permits the assessment of Ura and 5FU plasma concentrations with detection limits pf 0.0245 and 0.0484 ng mL(-1) (RSD = 1.0-2.5%, S/N = 3), respectively, without any problems of non-specific false-positives and cross-reactivities in complicated matrices of biological samples.
authors.affiliation: Department of Chemistry, Analytical Division, Faculty of Science, Banaras Hindu University, Varanasi, India. prof.bbpd@yahoo.com
authors.forename: Bhim Bali
authors.initials: BB
authors.lastname: Prasad
authors.forename: Khushaboo
authors.initials: K
authors.lastname: Tiwari
authors.forename: Meenakshi
authors.initials: M
authors.lastname: Singh
authors.forename: Piyush Sindhu
authors.initials: PS
authors.lastname: Sharma
authors.forename: Amit Kumar
authors.initials: AK
authors.lastname: Patel
authors.forename: Shrinkhala
authors.initials: S
authors.lastname: Srivastava
mesh_terms: D001557:Benzenesulfonates / Q000737:chemistry; D001665:Binding Sites; D054067:Dihydropyrimidine Dehydrogenase Deficiency / Q000175:diagnosis; D005472:Fluorouracil / Q000032:analysis* / Q000097:blood / Q000302:isolation & purification; D006801:Humans; D008855:Microscopy, Electron, Scanning; D054802:Molecular Imprinting / Q000191:economics / Q000295:instrumentation / Q000379:methods*; D011108:Polymers / Q000737:chemistry; D012680:Sensitivity and Specificity; D052617:Solid Phase Microextraction / Q000191:economics / Q000295:instrumentation / Q000379:methods*; D012997:Solvents / Q000737:chemistry; D017550:Spectroscopy, Fourier Transform Infrared; D013499:Surface Properties; D014498:Uracil / Q000032:analysis* / Q000097:blood / Q000302:isolation & purification
chemical_list: D001557:Benzenesulfonates; D011108:Polymers; D012997:Solvents; C056082:4-sulfophenylmethallyl ether; D014498:Uracil; D005472:Fluorouracil