A Kinetic Study on Enhanced Cementation of Gold Ions by Galvanic Interactions between Aluminum (Al) as an Electron Donor and Activated Carbon (AC) as an Electron Mediator in Ammonium Thiosulfate System

The enhanced cementation technique by galvanic interaction of aluminum (Al; electron donor) and activated carbon (AC; electron mediator) to recover gold (Au) ions from the ammonium thiosulfate solution is a promising technique to eliminate the challenges of poor recovery in the system. This study presents the kinetics of Au ion cementation in an ammonium thiosulfate lixiviant as functions of initial Au concentration, size/amount of Al and AC, temperature, and shaking speed. The recovery results basically followed first order kinetics and showed that the cementation rate increased with a higher initial concentration of Au, smaller electron donor size, greater both electron donor and mediator quantity, decrease in temperature, and higher shaking speed in the system, while size of electron mediator did not significantly affect Au recovery.

CMOS-Based Redox-Type Label-Free ATP Image Sensor for In Vitro Sensitive Imaging of Extracellular ATP

Adenosine 5′-triphosphate (ATP) plays a crucial role as an extracellular signaling molecule in the central nervous system and is closely related to various nerve diseases. Therefore, label-free imaging of extracellular ATP dynamics and spatiotemporal analysis is crucial for understanding brain function. To decrease the limit of detection (LOD) of imaging extracellular ATP, we fabricated a redox-type label-free ATP image sensor by immobilizing glycerol-kinase (GK), L-α-glycerophosphate oxidase (LGOx), and horseradish peroxidase (HRP) enzymes in a polymer film on a gold electrode-modified potentiometric sensor array with a 37.3 µm-pitch. Hydrogen peroxide (H2O2) is generated through the enzymatic reactions from GK to LGOx in the presence of ATP and glycerol, and ATP can be detected as changes in its concentration using an electron mediator. Using this approach, the LOD for ATP was 2.8 µM with a sensitivity of 77 ± 3.8 mV/dec., under 10 mM working buffers at physiological pH, such as in in vitro experiments, and the LOD was great superior 100 times than that of the hydrogen ion detection-based image sensor. This redox-type ATP image sensor may be successfully applied for in vitro sensitive imaging of extracellular ATP dynamics in brain nerve tissue or cells.

Role of Iron Phthalocyanine Coordination in Catecholamines Detection

Catecholamines are an important class of neurotransmitters responsible for regularizing, controlling, and treating neural diseases. Based on control and diseases treatment, the development of methodology and dives to sensing is a promissory technology area. This work evaluated the role of iron phthalocyanine coordination (FePc) with the specific groups from catecholamine molecules (L-dopa, dopamine, epinephrine, and the amino acid tyrosine) and the effect of this coordination on electrochemical behavior. The in situ coordination analysis was performed through isotherms π-A of FePc Langmuir films in the absence and presence of catecholamines. The π-A isotherm indicates a strong interaction between FePc monolayer and L-Dopa and DA, which present a catechol group and a side chain with a protonated amino group (-NH3+). These strong interactions with catechol and amine groups were confirmed by characterization at the molecular level using the surface-enhanced Raman spectroscopy (SERS) from a Langmuir–Schaefer monolayer deposited onto Ag surfaces. The electrochemical measurements present a similar tendency, with lower oxidation potential observed to DA>L-Dopa>Ep. The results corroborate that the coordination of the analyte on the electron mediator surface plays an essential role in an electrochemical sensing application. The FePc LS film was applied as a sensor in tablet drug samples, showing a uniformity of content of 96% for detecting active compounds present in the L-Dopa drug samples.

Redox Sensor Array with 23.5-μm Resolution for Real-Time Imaging of Hydrogen Peroxide and Glutamate Based on Charge-Transfer-Type Potentiometric Sensor

Towards clarifying the spatio-temporal neurotransmitter distribution, potentiometric redox sensor arrays with 23.5-µm resolution were fabricated. The sensor array based on a charge-transfer-type potentiometric sensor comprises 128×128 pixels with gold electrodes deposited on the surface of pixels. The sensor output corresponding to the interfacial potential of the electrode changed logarithmically with the mixture ratio of K3Fe(CN)6 and K4Fe(CN)6, where the redox sensitivity reached 49.9 mV/dec. By employing hydrogen peroxidase as an enzyme and ferrocene as an electron mediator, the sensing characteristics for hydrogen peroxide (H2O2) were investigated. The analyses of the sensing characteristics revealed that the sensitivity was about 44.7 mV/dec., comparable to the redox sensitivity, while the limit of detection (LOD) was achieved to be 1 µM. Furthermore, the oxidation state of the electron mediator can be the key to further lowering the LOD. Then, by immobilizing oxidizing enzyme for H2O2 and glutamate oxidase, glutamate (Glu) measurements were conducted. As a result, similar sensitivity and LOD to those of H2O2 were obtained. Finally, the real-time distribution of 1 µM Glu was visualized, demonstrating the feasibility of our device as a high-resolution bioimaging technique.

Electron Mediation and Photocurrent Enhancement in Dunalliela salina Driven Bio-Photo Electrochemical Cells

In recent years, finding alternatives for fossil fuels has become a major concern. One promising solution is microorganism-based bio-photo electrochemical cells (BPECs) that utilize photosynthetic solar energy conversion as an energy source while absorbing CO2 from the atmosphere. It was previously reported that in cyanobacterial-based BPECs, the major endogenous electron mediator that can transfer electrons from the thylakoid membrane photosynthetic complexes and external anodes is NADPH. However, the question of whether the same electron transfer mechanism is also valid for live eukaryotic microalgae, in which NADPH must cross both the chloroplast outer membrane and the cell wall to be secreted from the cell has remained elusive. In this work, we show that NADPH is also the major endogenous electron mediator in the microalgae Dunalliela salina (Ds). We show that the ability of Ds to tolerate high salinity enables the production of a photocurrent that is 5–6 times greater than previously reported for freshwater cyanobacterial-based BPECs in the presence or absence of exogenous electron mediators. Additionally, we show that the electron mediator Vitamin B1 can also function as an electron mediator enhancing photocurrent production. Finally, we show that the addition of both FeCN and NADP+ to Ds has a synergistic effect enhancing the photocurrent beyond the effect of adding each mediator separately.

Photoelectrochemical Oxidation in Ambient Conditions Using Earth-Abundant Hematite Anode: A Green Route for the Synthesis of Biobased Polymer Building Blocks

This study demonstrates the use of a photoelectrochemical device comprising earth-abundant hematite photoanode for the oxidation of 5-hydroxymethylfurfural (5-HMF), a versatile bio-based platform chemical, under ambient conditions in the presence of an electron mediator. The results obtained in this study showed that the hematite photoanode, upon doping with fluorine, can oxidize water even at lower pH (4.5 and 9.0). For 5-HMF oxidation, three different pH conditions were investigated, and complete oxidation to 2,5-furandicarboxylic acid (FDCA) via 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) was achieved at pH above 12. At lower pH, the oxidation followed another route via 2,5-diformylfuran (DFF), yielding 5-formyl-2-furancarboxylic acid (FFCA) as the main product. Using the oxidized intermediates as substrates showed DFF to be most efficiently oxidized to FDCA. We also show that, at pH 4.5, the addition of the laccase enzyme promoted the oxidation of 5-HMF to FFCA.

Effect of Geobacter metallireducens nanowire on electron transfer efficiency in MFC

Inhibitory effect of electron mediator AQDS on Geobacter metallireducens nanowire in microbial fuel cell (MFC) was studied. In the culture process of G. metallireducens with Fe(OH)3 as electron acceptor, the concentration of reduction product Fe (II) in solution without AQDS is higher than that with AQDS after 10 days, due to the formation of microbial nanowires. The effects of nanowire on electron transfer efficiency and power generation characteristic were studied using double chamber MFC reactor. The transfer efficiency between biofilm and electrodes was increased by nanowire, which increases maximum output voltage of MFC from 321 mV to 442 mV. The nanowire biofilm electrode has the bigger cyclic voltammetry curve peak, smaller activation resistance and stronger current response signal through electrochemical measurement, which indicated that the nanowire enhanced the electrochemical activity of the electrode.