title: The fate of differently functionalized gold nanorods in human serum: A response from capillary electrophoresis-inductively coupled plasma mass spectrometry.
abstract: A highly selective and sensitive method was developed to characterize intrinsic intramolecular interactions between potential theranostic agents, gold nanorods (AuNRs), and plasma proteins. The method is based on a hyphenation of capillary electrophoresis (CE) with inductively coupled plasma mass spectrometry (ICP-MS), which enables monitoring the speciation changes of AuNRs under physiologically compatible conditions. To improve the separation resolution between the intact nanorods and different gold-protein conjugates, the CE system was optimized by varying the type and concentration of background electrolyte, applied voltage, and sample loading. Optimization allowed also for acquiring the acceptable figures of merit such as migration time and peak area precision of 4.7-8.2% and 5.1-6.3%, respectively, detection limits in the range of 5.5-5.7μgL-1Au, and recoveries on the order of 91-99%. With the developed method the metal-specific profiles were recorded for differently functionalized AuNPs in combinations with individual serum proteins and in human serum. In case of carboxy-modified AuNPs, proteinization in real-serum environment occurs without albumin participation, apo-transferrin dominating the protein corona under equilibrium conditions. On the contrary, the AuNRs with surface amino-groups first form the albumin conjugate but albumin in this "soft" corona becomes slowly replaced by other, less abundant proteins, exhibiting a higher affinity toward the aminated surface.
authors.affiliation: Chair of Analytical Chemistry, Faculty of Chemistry, Warsaw University of Technology, 00-664 Warsaw, Poland. Electronic address: mmatczuk@ch.pw.edu.pl.
authors.forename: Magdalena
authors.initials: M
authors.lastname: Matczuk
authors.affiliation: Chair of Analytical Chemistry, Faculty of Chemistry, Warsaw University of Technology, 00-664 Warsaw, Poland.
authors.forename: Joanna
authors.initials: J
authors.lastname: Legat
authors.affiliation: Department of Chemistry "Ugo Schiff", University of Florence, 50019 Florence, Italy.
authors.forename: Federica
authors.initials: F
authors.lastname: Scaletti
authors.affiliation: Department of Chemistry "Ugo Schiff", University of Florence, 50019 Florence, Italy.
authors.forename: Luigi
authors.initials: L
authors.lastname: Messori
authors.affiliation: Chair of Analytical Chemistry, Faculty of Chemistry, Warsaw University of Technology, 00-664 Warsaw, Poland; Vernadsky Institute of Geochemistry and Analytical Chemistry, 119991 Moscow, Russian Federation.
authors.forename: Andrei R
authors.initials: AR
authors.lastname: Timerbaev
authors.affiliation: Chair of Analytical Chemistry, Faculty of Chemistry, Warsaw University of Technology, 00-664 Warsaw, Poland.
authors.forename: Maciej
authors.initials: M
authors.lastname: Jarosz
mesh_terms: D001798:Blood Proteins / Q000737:chemistry*; D019075:Electrophoresis, Capillary / Q000379:methods; D006046:Gold / Q000737:chemistry*; D006801:Humans; D013058:Mass Spectrometry / Q000379:methods; D043942:Nanotubes / Q000737:chemistry*; D044967:Serum / Q000737:chemistry*
chemical_list: D001798:Blood Proteins; D006046:Gold
keywords: CE-ICP-MS; Gold nanorods; Human serum; Protein corona