Trivalent Copper Ion-Mediated Dual Oxidation in the Copper-Catalyzed Fenton-Like System in the Presence of Histidine.

The Cu(II)/H2O2 system is recognized for its potential to degrade recalcitrant organic contaminants and inactivate microorganisms in wastewater. We investigated its unique dual oxidation strategy involving the selective oxidation of copper-complexing ligands and enhanced oxidation of nonchelated organic compounds. L-Histidine (His) and benzoic acid (BA) served as model compounds for basic biomolecular ligands and recalcitrant organic contaminants, respectively. In the presence of both His and BA, the Cu(II)/H2O2 system rapidly degraded His complexed with copper ions within 30 s; however, BA degraded gradually with a 2.3-fold efficiency compared with that in the absence of His. The primary oxidant responsible was the trivalent copper ion [Cu(III)], not hydroxyl radical (•OH), as evidenced by •OH scavenging, hydroxylated BA isomer comparison with UV/H2O2 (a •OH generating system), electron paramagnetic resonance, and colorimetric Cu(III) detection via periodate complexation. Cu(III) selectively oxidized His owing to its strong chelation with copper ions, even in the presence of excess tert-butyl alcohol. This selectivity extended to other copper-complexing ligands, including L-asparagine and L-aspartic acid. The presence of His facilitated H2O2-mediated Cu(II) reduction and increased Cu(III) production, thereby enhancing the degradation of BA and pharmaceuticals. Thus, the Cu(II)/H2O2 system is a promising option for dual-target oxidation in diverse applications.

Electrochemical production of hydroxylamine from nitrate on metal electrodes: A comparative study of selectivity and efficiency.

Despite the great potential of electrochemical nitrate reduction as a hydroxylamine production method, this strategy has not been sufficiently examined, and the effects of electrode material type on the selectivity and efficiency of this reduction remain underexplored. To bridge this gap, the present study evaluated six metals (Ag, Cu, Ni, Sn, Ti, and Zn) as cathode materials for the electrochemical reduction of nitrate to hydroxylamine, showing that the selectivity of hydroxylamine production was maximal for Sn, while the corresponding faradaic and energy utilization efficiencies were maximal for Ti. Although all tested materials favored nitrate reduction over hydrogen evolution, the disparity in the onset potentials of these reactions did not adequately explain the variations in nitrate removal efficiency, which was found to be influenced by material resistance and charge-transfer properties. The rate constants of elementary nitrate reduction steps determined from the time-dependent concentrations of nitrate and its reduction products (nitrous acid, hydroxylamine, and ammonium) were used to calculate the selectivity and efficiency of hydroxylamine production for each electrode. In turn, these selectivities and efficiencies were correlated with the density functional theory-computed adsorption energies of a key hydroxylamine precursor on different electrodes to afford a volcano-type plot with Ti and Sn at its pinnacle. Thus, this study introduces valuable descriptors and methods for the further screening of electrocatalysts for hydroxylamine generation and the establishment of more environmentally friendly hydroxylamine production techniques utilizing sustainable electricity.

Cupric ion in combination with hydrogen peroxide and hydroxylamine applied to inactivation of different microorganisms.

The microbial inactivation by cupric ion (Cu(II)) in combination with hydrogen peroxide (H2O2) and hydroxylamine (HA) was investigated for twelve different microorganisms (five Gram-negative bacteria, three Gram-positive bacteria, and four bacteriophages). The inactivation efficacy, protein oxidation, and RNA (or DNA) damage were monitored during and after treatment by Cu(II), Cu(II)/HA, Cu(II)/H2O2 and Cu(II)/HA/H2O2. The rate of microbial inactivation by the (combined) microbicides generally increased in the order of Cu(II) < Cu(II)/H2O2 < Cu(II)/HA < Cu(II)/HA/H2O2; Cu(II)/HA/H2O2 resulted in 0.18-0.31, 0.10-0.18, and 0.55-3.83 log inactivation/min for Gram-negative bacteria, Gram-positive bacteria, and bacteriophages, respectively. The degrees of protein oxidation and RNA (or DNA) damage increased in the order of Cu(II) < Cu(II)/HA < Cu(II)/H2O2 < Cu(II)/HA/H2O2. In particular, Cu(II)/HA/H2O2 led to exceptionally fast inactivation of the viruses. Gram-positive bacteria tended to show higher resistance to microbicides than other microbial species. The microbicidal effects of the combined microbicides on the target microorganisms were explained by the roles of Cu(I) and Cu(III) generated by the redox reactions of Cu(II) with H2O2, HA, and oxygen. Major findings of this study indicate that Cu(II)-based combined microbicides are promising disinfectants for different waters contaminated by pathogenic microorganisms.

Chemically responsive nanoporous pigments: colorimetric sensor arrays and the identification of aliphatic amines.

A general method has been developed for the preparation of microspheres of nanoporous pigments, their formulation into chemically responsive pigment inks, and the printing of these inks as colorimetric sensor arrays. Using an ultrasonic-spray aerosol-gel synthesis from chemically responsive dyes and common silica precursors, 16 different nanoporous pigment microspheres have been prepared and characterized. New colorimetric sensor arrays have been created by printing inks of these chemically responsive pigments as primary sensor elements; these arrays have been successfully tested for the detection, identification, and quantitation of toxic aliphatic amines. Among 11 structurally similar amines, complete identification of each analyte without confusion was achieved using hierarchical cluster analysis (HCA). Furthermore, visual identification of ammonia gas was easily made at the IDLH (immediately dangerous to life or health), PEL (permissible exposure limits), and 0.1 PEL concentrations with high reproducibility.

A colorimetric sensor array for detection and identification of sugars.

Molecular recognition of sugars and a practical method to detect and discriminate among a large number of such similar analytes remain substantial scientific challenges. We report here a low-cost, simple colorimetric sensor array capable of identification and quantification of sugars and related compounds. Fifteen different monosaccharides, disaccharides, and artificial sweeteners were differentiated without error in 80 trials. Limits of detection at pH 7.4 for glucose were <1 mM, which is below physiologically important levels.