A Novel Supramolecular Assembly Film of Porphyrin Bound DNA: Characterization and Catalytic Behaviors Towards Nitric Oxide

Abstract

Chronoamperometric experiments demonstrated a rapid response to the reduction of NO with a linear range from 0.1 to 90 µM and a detection limit of 30 nM at a signal-to-noise ratio of 3. On the other hand, it is the first time to apply high-valent iron porphyrin as catalyst at modified electrode for NO catalytic oxidation at +0.89 vs. Ag|AgCl. The sensor shows a high selectivity of some endogenous electroactive substances in biological systems. The mechanism of response of the sensors to NO is preliminary studied.

Nitric Oxide Detection Using Electrochemical Third‐generation Biosensors – Based on Heme Proteins and Porphyrins

“…They are relatively inexpensive and have good stability in solution . Other chemical groups, such as metalloporphyrins have been also tested in NO biosensors; formal potentials in the range of −0.338 to −0.130 V vs. SCE have been reported. A cathodic and an anodic peak were attributed to the Fe(III)/Fe(II) couple of hemin at −0.370±0.012 V and −0.305±0.019 V vs. SCE, respectively, corresponding to the lowest E°′ of −0.338 V vs. SCE at an hemin‐MWCNTs‐chitosan using carbon fiber microelectrodes (CFM) .…”

“…The iron(III) meso‐tetrakis(N‐methylpyridinium‐4‐yl)porphyrin (Fe(4‐TMPyP) was used to prepare a novel Fe(4‐TMPyP) biosensor with Fe(4‐TMPyP) immobilized with DNA and poly(acrylamide‐co‐diallyldimethylammonium chloride (PADDA), forming a DNA‐bound‐porphyrin complex more stable and biocompatible. The developed complex showed the highest transfer rate (k s =3.12 s −1 ) and consequently the highest E°′ of −0.130 V vs. SCE . The peak potentials of the Fe(III)/Fe(II) couple are in agreement with the other related studies (Table ) supporting the DET of porphyrins .…”

“…Some factors could have influenced these two different pathways including the mode of the electron transfer to the heme group, the residues surrounding the heme groups and the pH of the solution and more important the way in which a second NO bind to the active site . In porphyrin based‐biosensors, a E cat from −0.776 to −0.566 V vs. SCE was reported for metalloporphyrins (Mn and Co)‐PP‐TBABF 4 /CFM and Fe(4‐TMPyP)‐DNA‐PADDA/PGE , respectively. Fe(4‐TMPyP) influenced positively the electron transfer rate and the detected value was, in this way, more positive.…”

“…A similar linear range was presented for MP (with values of 1.0–40 μM for MP‐CAS‐SOD‐MWCNTs‐PTTCA‐AuNPs/GCE) . For hemin biosensors, large linear ranges (0.1–90 μM ; 0.5–50 μM ) were described with the exception for the hemin‐MWCNTs‐Chitosan/CFM biosensor (0.25–1.0 μM) showing the advantages of the utilization of microelectrodes (in this case carbon fiber microelectrode) to reach low NO determination levels.…”

Mechanistic Aspects of Photoinactivation of Candida albicans by Exogenous Porphyrins†

“…4, upper left panel). Several researchers have demonstrated that the binding of cationic porphyrins to DNA is presumably stabilized by an electrostatic interaction between the positive charges on the porphyrin’s periphery and the negatively charged phosphate group of DNA (36). TMPyP‐DNA binding appears to correspond to the steric electrostatic potential in GC‐rich regions on the DNA (28,37–39).…”