Gold nanoparticles embedded electropolymerized thin film of pyrimidine derivative on glassy carbon electrode for highly sensitive detection of l-cysteine.

This paper demonstrates the fabrication of novel gold nanoparticles incorporated poly (4-amino-6-hydroxy-2-mercaptopyrimidine) (Nano-Au/Poly-AHMP) film modified glassy carbon electrode and it is employed for highly sensitive detection of l-cysteine (CYS). The modified electrode was characterized by scanning electron microscope (SEM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). SEM images of modified electrode revealed the homogeneous distribution of gold nanoparticles on poly (4-amino-6-hydroxy-2-mercaptopyrimidine) thin film modified glassy carbon electrode. The modified electrode was successfully utilized for highly selective and sensitive determination of l-cysteine at physiological pH7.0. The present electrochemical sensor successfully resolved the voltammetric signals of ascorbic acid (AA) and l-cysteine with peak separation of 0.510V. To the best of our knowledge, this is the first report of larger peak separation between AA and CYS. Wide linear concentration ranges (2µM-500µM), low detection limit (0.020µM), an excellent reproducibility and stability are achieved for cysteine sensing with this Nano-Au/Poly-AHMP/GCE.

Generating monomeric 5-coordinated microperoxidase-11 using carboxylic acid functionalized silver nanoparticles: A surface-enhanced resonance Raman scattering analysis.

Microperoxidase-11 (MP-11), a heme undecapeptide obtained by proteolytic digestion of cytochrome c, resembles peroxidase enzyme when its heme center is 5-coordinated with a vacant sixth coordination site. However, MP-11 always tends to aggregate in both solution and on surface and eventually forms the 6-coordinated heme. Thus, the present study investigates the immobilization strategy of MP-11 on nanoparticle surface in order to generate monomeric 5-coordinated MP-11 and make them as an efficient biocatalyst. The powerful surface-enhanced resonance Raman scattering (SERRS) technique is being employed to attain the detailed structural information of the catalytic site i.e., the heme center. The localized surface plasmon resonance (LSPR) tuned and 6-mercaptohexanoic acid (MHA) functionalized silver nanoparticles (Ag@MHA NPs) are used as Raman signal amplifier. The outcome of the SERRS study unambiguously portrays the existence of monomeric 5-coordinated MP-11 on Ag@MHA NPs surface. Here, Ag@MHA NPs plays a dual role of providing a platform to create monomeric 5-coordinated MP-11 and to load large number of MP-11 due to its high surface to volume ratio. Further, the electrostatic interaction between Ag@MHA NPs and MP-11 leads to instantaneous SERRS signal enhancement with a Raman enhancement factor (EFSERS) of 2.36×10(6). Langmuir adsorption isotherm has been employed for the adsorption of MP-11 on Ag@MHA NPs surface, which provides the real surface coverage (ΓS(*)) and equilibrium constant (K) value of 1.54nm and 5×10(11)M(-1). Furthermore, the peroxidase activity of MP-11 has been demonstrated through electrocatalytic oxygen reduction reaction.

Plasmon-tuned silver colloids for SERRS analysis of methemoglobin with preserved nativity.

Optically tuned silver nanoparticles (AgNP's) functionalized with ω-mercaptoalkanoic acids are synthesized and used as a signal amplifier for the surface-enhanced resonance Raman scattering (SERRS) study of heme cofactor in methemoglobin (metHb). Even though both mercaptopropionic acid (MPA)- and mercaptononanoic acid (MNA)-functionalized AgNP's exemplify vastly enhanced SERRS signal of metHb, MNA-AgNP's amplify the SERRS signal amid preservation of the nativity of the heme pocket, unlike MPA-AgNP's. The electrostatic interaction between MNA-AgNP's and metHb leads to instant signal enhancement with a Raman enhancement factor (EF(SERS)) of 4.2 × 10(3). Additionally, a Langmuir adsorption isotherm has been employed for the adsorption of metHb on the MNA-AgNP surface, which provides the real surface coverage and equilibrium constant (K) of metHb as 139 nM and 3.6 × 10(8) M(-1), respectively. The lowest detection limit of 10 nM for metHb has been demonstrated using MNA-AgNP's besides retaining the nativity of the heme pocket.