Elucidating the Electrochemical Mechanism of NG-Hydroxy-L-arginine.

NG-Hydroxy-L-arginine (NOHA) is a stable intermediate product in the urea cycle that can be used to monitor the consumption of L-arginine by nitrous oxide synthase (NOS) to produce nitric oxide (NO) and L-citrulline. Research has implicated the urea cycle in many diseases and NO has cultivated interest as a potential biomarker for neural health. Electrochemical detection is an established, cost-effective method that can successfully detect low levels of analyte concentrations. As one of the few electrochemically active species in the urea cycle, NOHA shows promise as a biomarker for monitoring disruptions in this biochemical process. In this study, we show that NOHA has an oxidation peak at +355 mV vs Ag/AgCl at a glassy carbon electrode. In addition, cyclic voltammetry studies with structural analogs - alanine and N-hydroxyguanidine - allowed us to approximate the oxidation wave at +355 mV vs Ag/AgCl to be a one electron process. Diffusivity of NOHA was found using linear scan voltammetry with a rotating disk electrode and approximated at 5.50×10-5 cm2/s. Ample work is still needed to make a robust biosensor, but the results here characterize the electrochemical activity and represent principle steps in making a NOHA biosensor.

Evaluation of Metal Oxide Surface Catalysts for the Electrochemical Activation of Amino Acids.

Electrochemical detection of amino acids is important due to their correlation with certain diseases; however, most amino acids require a catalyst to electrochemically activate. One common catalyst for electrochemical detection of amino acids are metal oxides. Metal oxide nanoparticles were electrodeposited onto glassy carbon and platinum working electrodes. Cyclic voltammetry (CV) experiments in a flow cell were performed to evaluate the sensors' ability to detect arginine, alanine, serine, and valine at micromolar and nanomolar concentrations as high as 4 mM. Solutions were prepared in phosphate buffer saline (PBS) and then 100 mM NaOH. Specifically, NiO surfaces were responsive to amino acids but variable, especially when exposed to arginine. Polarization resistance experiments and scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS) data indicated that arginine accelerated the corrosion of the NiO catalyst through the formation of a Schiff base complex.

Porphyrin-Cored Polymer Nanoparticles: Macromolecular Models for Heme Iron Coordination.

Porphyrin-cored polymer nanoparticles (PCPNs) were synthesized and characterized to investigate their utility as heme protein models. Created using collapsible heme-centered star polymers containing photodimerizable anthracene units, these systems afford model heme cofactors buried within hydrophobic, macromolecular environments. Spectroscopic interrogations demonstrate that PCPNs display redox and ligand-binding reactivity similar to that of native systems and thus are potential candidates for modeling biological heme iron coordination.