Real-Time Electrochemical Detection of Uric Acid, Dopamine and Ascorbic Acid by Heme Directly Modified Carbon Electrode.

Several simple electrochemical sensors were designed for three analytes, uric acid (UA), dopamine (DA) and ascorbic acid (AA) detection via electrolytic deposition of three functional materials heme, Fc(Cys)2 and Fc-ECG onto glassy carbon electrodes (GCEs) without other medium. Characterization of the modified GCEs was conducted using SEM, TEM and DPV methods. Results showed that the heme/GCE demonstrated notable electro-catalytic capabilities, towards DA, AA, and UA oxidation in a solution of phosphate buffer. The current signals of DPV technique for three analytes shown up three defined oxidated peaks, the peak potential differences was 192 mV for AA and DA, and 142 mV for DA and UA. Under optimal conditions, it can be obtained linear responses for AA, DA and UA in the following concentration ranges: 10 to 50, 5 to 20, and 2.5 to 20 µmol·L-1, and the limits of detection was calculated as 0.76, 0.50 and 0.63 µmol·L-1, respectively. The results demonstrated that the heme directly modified GCE was a well-suited electrochemical sensor for determining UA, DA and AA in actual samples.

The construction of a simple sensor for the simultaneous detection of nitrite and thiosulfate by heme catalysis.

Several simple sensors were fabricated through a one-step method. By depositing electro-active compounds, such as ß-cyclodextrins (ß-CD), heme, dopamine (DA), or Fc-ECG, onto a screen-printed electrode (SPE), the successful simultaneous detection of nitrite (NO2 -) and thiosulfate (S2O3 2-) ions was observed. Under optimal operating conditions, the notable electrocatalytic abilities of a Heme/SPE sensor were detected for the oxidation of NO2 - and S2O3 2-, with remarkable peak potential differences, after characterization via SEM, CV, and DPV. Linear relationships were obtained in the ranges of 5.0-200.0 µmol L-1 and 1.0-100.0 µmol L-1 for the current response versus concentration of NO2 - and S2O3 2-, respectively. The limits of detection were determined to be 1.67 and 0.33 µmol L-1 while the sensitivities of detection were noted to be 0.43 and 1.43 µA µM-1 cm-2, respectively. During the detection of NO2 - and S2O3 2-, no interfering common ions were observed. Furthermore, average recoveries from 96.0 to 104.3% and a total R.S.D. of less than 3.1% were found for the detection of NO2 - and S2O3 2- in pickled juice and tap water using the simple sensor. These results showed that rapid and precise measurements for actual application in NO2 - and S2O3 2- detection could be conducted in food samples, indicating a potential use in food safety.

A Facile Electrochemical Sensor Labeled by Ferrocenoyl Cysteine Conjugate for the Detection of Nitrite in Pickle Juice.

Simple and facile electrochemical sensors for nitrite detection were fabricated by directly depositing ferrocenoyl cysteine conjugates Fc[CO-Cys(Trt)-OMe]2 [Fc(Cys)2] or Fc[CO-Glu-Cys-Gly-OH] [Fc-ECG] on screen-printed electrodes (SPEs). The modified carbon electrodes were characterized by scanning electron microscopy (SEM), cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Results indicated that Fc-ECG/SPE sensor showed enhanced current response and a lower overpotential than Fc(Cys)2/SPE sensor for nitrite detection. Optimal operating conditions were estimated for nitrite detection by DPV. The concentration of nitrite showed a good linear relationship with the current response in the range of 1.0⁻50 µmol·L-1 and with 0.3 µmol·L-1 as the concentration for limit of detection. There were no interferences from most common ions. The development of this electrochemical sensor was used for nitrite detection in pickled juice with a R.S.D. lower than 2.1% and average recovery lower than 101.5%, which indicated that disposable electrochemical sensor system can be applied for rapid and precise nitrite detection in foods.

AgI -Induced Switching of DNA Binding Modes via Formation of a Supramolecular Metallacycle.

The histidine derivative L1 of the DNA intercalator naphthalenediimide (NDI) forms a triangular AgI complex (C2). The interactions of L1 and of C2 with DNA were studied by circular dichroism (CD) and UV/Vis spectroscopy and by viscosity studies. Different binding modes were observed for L1 and for C2, as the AgI complex C2 is too large in size to act as an intercalator. If AgI is added to the NDI molecule that is already intercalated into a duplex, higher order complexes are formed within the DNA duplex and cause disruptions in the helical duplex structure, which leads to a significant decrease in the characteristic CD features of B-DNA. Thus, via addition of a metal we show how a classic and well-known organic intercalator unit can be turned into a partial metallo insertor. We also show how electrochemical impedance spectroscopy (EIS) can be used to probe DNA binding modes on DNA films that are immobilized on gold surfaces.

On the Role of Chirality in Guiding the Self-Assembly of Peptides.

Homochirality in peptides is crucial in sustaining "like-like" intermolecular interactions that allow the formation of assemblies and aggregates and is ultimately responsible for the resulting material properties. With the help of a series of stereoisomers of the tripeptide F-F-L, we demonstrate the critical role that peptide stereochemistry plays in the self-assembly of peptides, guided by molecular recognition, and for self-sorting. Homochiral self-assemblies are thermally and mechanically more robust compared to heterochiral self-assemblies. Morphological studies of the multicomponent peptide systems showed that aggregates formed from homochiral peptides possessed a uniform nano-fibrous structure, whereas heterochiral systems resulted in self-sorted systems with a heterogeneous morphology. In essence, homochiral peptides form the stronger aggregates, which may be one of reasons why homochirality is preferred in living systems.

Metal coordination of ferrocene-histidine conjugates.

This study presents a few bis(histidine) ligands working to build a small peptidic model system of zinc structural sites. Ferrocene-peptide conjugates Fc[CO-His(Trt)-His(Trt)-OMe]2 (3), Fc[CO-His(Trt)-Asp(OMe)-OMe]2 (4), and Fc[CO-His(Trt)-Glu(OMe)-OMe]2 (5) were synthesized and characterized spectroscopically. 1H-NMR and IR spectroscopic studies reveal hydrogen bonding interactions and while more detailed circular dichroism studies show a 1,2'-P helical "Herrick conformation" for Fc-conjugates 4 and 5, we discovered M-helical chirality in Fc-peptide 3. The half-wave potentials (E1/2) of ferrocene-peptides follow the sequence 3 < 5 < 4 which is rationalized by the capability of the peptide side chains to stabilize the oxidized ferrocene-peptide form. The diffusion coefficient (D) and electron transfer rate constant (ksh) values for all Fc-conjugates were determined by their resultant cyclic voltammetry data. The interactions for all Fc-conjugates were probed with metal ions Zn2+, Cd2+, Ni2+, Cu2+, Mn2+, and Mg2+ which were detected to interact at 1 : 1 ratio between the ligand and metal ion verified by 1H-NMR and UV titration studies, electrochemical investigations, and ESI-MS experiments. Electrochemical studies for all Fc-conjugates exhibit anodic potential shifts upon the addition of metal ions, which follow the order Cu2+ > Zn2+ > Ni2+ > Cd2+ > Mn2+ > Mg2+. NMR spectroscopic experiments show that the two nitrogen atoms present on each imidazole ring of His residues are the site of metal coordination. There is a strong indication that peptide conjugates 4 and 5 in the presence of Zn2+ enforce a coordination number of four as the CD spectra of Fc-conjugates 4 and 5 exhibited a red shift which corresponds to the third and fourth coordination sites occupied by neutral carbonyl oxygen donor atoms, in addition, carbonyl amide appears downward shifted in wavenumber upon metal addition.

A Ferrocene-Tryptophan Conjugate: The Role of the Indolic Nitrogen in Supramolecular Assembly.

Bio-organometallic ferrocene-containing amino acids and peptides have been reported to form gels and are interesting to study due to their structural properties and applications for biological purposes. In this study, a ferrocene-dicarboxylic acid derivative of the dipeptide tryptophan-tryptophan was investigated. The indolic nitrogen in the amino acid tryptophan is important for biological functions due to its role in hydrogen bonding. Here, intermolecular interactions with the indolic nitrogen allow this conjugate to self-assemble into a fibrous supramolecular structure that forms a stable gel. Rheological analysis demonstrates the self-healing nature of this gel. Interestingly, X-ray analysis of this ferrocene-peptide conjugate reveals close contacts involving tryptophan, in particular the indole NH group in interactions with an adjacent neighboring molecule.