Polyelectrolyte‐Functionalized Gold Nanoparticle Scaffold for the Sensing of Heparin and Protamine in Serum

Abstract

We describe a shape-controlled synthesis of polyelectrolyte-functionalized flowerlike and polyhedral Au nanoparticles and the development of a nanoarchitectured platform for the selective and highly sensitive detection of protamine and heparin by voltammetric, impedimetric, and microgravimetric techniques. The functionalized Au nanoparticles were chemically synthesized in aqueous solution at room temperature in the presence of the polyelectrolyte (either protamine or heparin). The charge on the polyelectrolyte controlled the shape and surface morphology of the nanoparticles. The negatively charged heparin-functionalized Au nanoparticles have multiple branched flowerlike shapes with an average size of 50 nm, whereas the cationic protamine-functionalized nanoparticles are of polyhedral shape with an average size of 25 nm. Both flowerlike and polyhedral nanoparticles have (111), (200), (220), and (311) planes of a face-centered cubic lattice of Au. Voltammetric, impedimetric, and microgravimetric sensing platforms based on functionalized Au nanoparticles have been developed for the sensing of heparin and protamine. The sensing platforms are developed by self-assembling the functionalized nanoparticles on a thiol-functionalized three-dimensional silicate network. The microgravimetric sensing platform shows very high sensitivity and it can detect heparin and protamine at concentrations as low as 0.05 μg mL(-1). The selectivity of the sensing platform towards heparin was examined with potential interferents such as hyaluronic acid (HA) and chondroitin-4-sulfate (CS). Both HA and CS did not interfere with the measurement of heparin. The practical application of the sensing platform was demonstrated by measuring the concentration of heparin and protamine in human serum samples. The sensing platform could successfully quantify the concentration of heparin and protamine in the real serum samples with excellent recovery. The sensing platform was robust and could be used for repeated measurement without compromising the sensitivity.

Title Monitoring Protamine‐Heparin Interactions Using Microcapillary Impedimetric Sensor

“…Various chemical sensors for heparin detection have been developed using appropriate signal transductions such as spectroscopy 3–5, voltammetry 6, 7, quartz microbalance 7, 8 and conductometry 9. The development of potentiometric polyion sensors was pioneered by M. Meyerhoff 10 and P. Bergveld in 1990’s 11 and more sophisticated methods based on application of pulsed chronopotentiometric polymer membrane electrode (pulstrode) 12, 13 and ion‐selective membranes operated by dynamic electrochemistry protocols 14 were successfully used for heparin determination later.…”

“…Selectivity of protamine‐heparin interaction was studied in many works and was demonstrated that it is possible to determine heparin concentration in human and animal serum 2, 4, 7, 18. The influence from blood electrolyte, serum albumin and g‐globulin in diluted samples is minimal.…”

Applications of scaffold-based advanced materials in biomedical sensing

“…Dey et al. [ 96 ] synthesized flower-like AuNP scaffolds for ultrasensitive detection of protamine and heparin in human serum samples. These scaffold materials were self-assembled on the surface of AuNPs and then attached to the surface of an electrochemical electrode using a thiol-functionalized 3D-silicate (3-(mercaptopropyl)trimethoxysilane (MPTS)) network.…”

Electrochemistry of surface wired cytochrome c and bioelectrocatalytic sensing of superoxide

“…31,32 Our group is interested in the development of electrochemical sensors for bioanalytes using the self-assemblies of organosulphur compounds and nanomaterials. [33][34][35][36] Recently, we have observed that the self-assembly of heterocyclic thiol promoted electron transfer for the redox reaction of microperoxidase-11. 36 In continuation of our research work, here we describe the electrochemistry of Cyt-c immobilized on the mixed self assembly of DTB and PET and the amperometric sensing of superoxide.…”