Convective Interaction Media Monolithic Chromatography with ICPMS and Ultraperformance Liquid Chromatography−Electrospray Ionization MS Detection: A Powerful Tool for Speciation of Aluminum in Human Serum at Normal Concentration Levels

Abstract

A new analytical procedure using separation support based on Convective Interaction Media (CIM) was developed for speciation of Al in human serum at normal concentration levels. The separation of proteins was performed on a weak anion exchange CIM diethylamine monolithic column. Isocratic elution with buffer A (0.05 M tris(hydroxymethyl)aminomethane-hydrochloric acid + 0.03 M sodium hydrogen carbonate) was applied for 5 min, followed by linear gradient elution from 100% buffer A to 100% buffer B (buffer A + 1 M ammonium chloride) for the next 40 min. Separation of proteins was followed by UV detection at 278 nm. Separated Al species were detected online by inductively coupled plasma mass spectrometry. It was experimentally proven that 91 +/- 7% of Al in human serum was eluted under the transferrin peak. Transferrin was identified on the basis of the retention volume and by ACQUITY ultraperformance liquid chromatography-electrospray ionization mass spectrometry. The problem of extraneous contamination with Al was successfully overcome by using efficient cleaning procedures of eluents and chromatographic supports. The efficient cleaning was of paramount importance to perform Al speciation at extremely low concentration levels. The repeatability of measurement tested for six consecutive separations of unspiked serum was +/-8.6%. The limits of detection and quantification (based on 3 and 10 s of the blank) were 0.15 and 0.49 ng mL(-1) Al bound to transferrin, respectively. This is the first report on quantitative and reliable speciation of Al in human serum at normal concentration levels.

New method for the speciation of ruthenium-based chemotherapeutics in human serum by conjoint liquid chromatography on affinity and anion-exchange monolithic disks

“…Due to such characteristics, monoliths are frequently used in chromatographic separations of biomolecules, organic acids and purification of viruses [28][29][30][31] while their use in speciation analysis is scarce. Examples of successful application of monolithic chromatography in speciation analysis are the investigations on Al speciation in human serum [32,33], Zn in human milk [34], Ni in tea infusions [35], the study of the distribution of cisplatin [36] in serum of cancer patients and the investigation of the kinetics of the interaction and distribution of Ptbased chemotherapeutics with proteins in blood serum [37]. In the study of the distribution of cisplatin in human serum [36], Pt fractionation was performed first by SEC on a HiTrap desalting column to separate unbound Pt from Pt bound to serum proteins.…”

Fluoride Alters Klk4 Expression in Maturation Ameloblasts through Androgen and Progesterone Receptor Signaling

“…in the use of the artificial serum replacement), provides indirect evidence to support this possibility. Aluminum is a trace element in the normal serum (Wang et al, 1991 ; Murko et al, 2009 ; Tomza-Marciniak et al, 2011 ), and it could explain why we see an effect of fluoride inhibiting AR nuclear translocation in serum containing media, but not in serum free media except with the addition of aluminum.…”

Pre-Column Derivatization HPLC Procedure for the Quantitation of Aluminium Chlorohydrate in Antiperspirant Creams Using Quercetin as Chromogenic Reagent

“…Hyphenated techniques by combining various chromatographic techniques with atomic spectrometry/mass spectrometry are the most efficient for the determination of aluminium in human body fluids [8, 9]. Recently, high-performance liquid chromatography interfaced to flame atomic spectrometry (HPLC–FAAS) [10] and a post-column derivatization procedure with 4,5-dihydroxy-1,3 benzene disulfonic acid disodium salt [11] have been used to quantify aluminium fluoride complexes in groundwater samples.…”