Copper(II) phthalocyanine as an electrocatalytic electrode for cathodic detection of urinary tryptophan.

Herein, we introduce a novel method for tryptophan detection via a reduction reaction facilitated by its interaction with a copper(II) phthalocyanine (CuPc) electrocatalytic electrode. This method addresses challenges associated with the susceptibility of the oxidation response to interference from various species when measuring tryptophan in bodily fluids. The reduction currents exhibit a linear increase with tryptophan concentrations in two ranges: 0.0013-0.10 mM and 0.10-1.20 mM, with the sensitivities of 14.7 ± 0.5 µA mM-1 and 3.5 ± 0.1 µA mM-1, respectively. The limit of detection (LOD, 3SB/m) is determined to be 0.39 µM. The sensor exhibits excellent reproducibility, with the relative standard deviation of <5%. Application of the sensor to authentic urine samples yields a % recovery of 101 ± 4%.

Determination of promethazine in forensic samples using multi-walled carbon nanotube-gold nanoparticle electrochemical sensor.

An electrochemical sensor was developed based on a glassy carbon electrode (GCE) modified with multi-walled carbon nanotubes (MWCNTs) and gold nanoparticles (AuNPs) for the determination of promethazine (PMZ) in 'purple drank', pharmaceutical formulations, and synthetic saliva. The oxidation of PMZ at the modified electrode occurred at a higher cathodic potential and produced a higher sensitivity compared to the unmodified GCE. The morphology of the modified electrode was characterized using field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDS), and transmission electron microscopy (TEM). The presence of MWCNTs and AuNPs was confirmed. The optimized parameters included the concentration and pH of the supporting electrolyte, amount of modifiers used to fabricate the electrode, deposition potential, and time. Using these optimized conditions, the method has a linear range from 0.5 to 100 µmol L-1, with a R2 value of 0.9991. The limit of detection (3SDblank/slope) was 0.13 µmol L-1. The proposed electrochemical sensor was successfully applied for the determination of PMZ in 'purple drank', pharmaceutical formulations, and spiked synthetic saliva samples. The results obtained from this sensor were in statistical agreement with the values obtained using the reference gas chromatography-flame ionization method.

Electrochemical detection of creatinine: exploiting copper(ii) complexes at Pt microelectrode arrays.

This work develops a rapid and highly sensitive electrochemical sensor for creatinine detection at platinum microelectrode arrays (Pt-MEA). Copper(ii) ions are introduced to form the electroactive creatinine complex, which is then detected at Pt-MEA through a direct reduction reaction. Electrochemical behaviors of the creatinine complex are also explored at Pt macrodisc and microdisc electrodes in comparison with Pt-MEA. At the Pt-MEA, the linear range, sensitivity, and limit of detection of creatinine are determined to be 0.00-5.00 mM, 5401 ± 99 A m-2 M-1, and 0.059 mM (3SB/m), respectively. Notably, the Pt-MEA requires only 10 µL of sample and allows direct measurement of creatinine in synthetic urine with 97.39 ± 4.78% recovery.

Benign electrolytic modifications of starch: effects on functional groups and physical properties.

Herein, a low-cost electrolytic technology for starch modification has been developed using abundant chloride salt as a redox mediator. The effects of electrolysis conditions on the in situ starch modification are investigated in detail, including chloride concentrations, applied voltages, and electrolysis durations. The modification mechanisms are determined by the type of chlorine species (Cl2, HClO, ClO-, and HCl) generated during the process. Following electrolysis, carbonyl and carboxyl groups ranging from 0.056 to 1.3 g/100 g of starch and 0.006 to 0.5 g/100 g of starch, respectively, were observed. Starch granule median size can be reduced from 15.3 µm to 13.5 µm. In addition to the pronounced changes in granule size, shape, and functional groups, electrolysis leads to increased moisture resistance, higher crystallinity, and substantial alterations in the pasting properties.

Methylene blue molecularly imprinted polymer for melatonin determination in urine and saliva samples.

A highly sensitive and rapid electrochemical sensor was developed for detecting melatonin using a molecularly imprinted polymer (MIP) with methylene blue as the functional monomer and melatonin as the template. The MIP was synthesized via a simple electropolymerization process that did not require an initiating reagent. The sensor demonstrated good selectivity for melatonin against common interferences such as lactate, cytosine, cytidine, urea, ascorbic acid, creatine, creatinine, serotonin, and tryptophan. Melatonin detection was achieved at a potential of 0.60 V vs. Ag/AgCl with a sensitivity of 138.8 ± 4.7 µA µM‒1 in the linear range 0.097 - 200 µM and a limit of detection of 29 nM (3SB/m). The sensor exhibited excellent reproducibility and repeatability for both within (intra) and between (inter) electrodes (%RSD < 3% for n = 3). The sensor was applied to authentic urine and saliva samples with recoveries of 103 ± 1% and 102 ± 1%, respectively.

Electrodeposited copper nanoparticles for creatinine detection via the in situ formation of copper-creatinine complexes.

Creatinine is an important biomarker of kidney diseases. In this work, a fast and facile electrochemical sensor was developed for creatinine detection based on the use of copper nanoparticle-modified screen-printed electrodes. The copper electrodes were prepared by simple electrodeposition of Cu2+ (aq). The electrochemically inactive creatinine was detected reductively via the in situ formation of copper-creatinine complexes. Two linear detection ranges, 0.28-3.0 mM and 3.0-20.0 mM, were achieved using differential pulse voltammetry, with the sensitivities of 0.824 ± 0.053 µA mM-1 and 0.132 ± 0.003 µA mM-1, respectively. The limit of detection was determined to be 0.084 mM. The sensor was validated in synthetic urine samples to yield 99.3% recovery (%RSD = 2.8), demonstrating high tolerance to possible interfering species. Finally, the stability of creatinine and its degradation kinetics at different temperatures were evaluated using our developed sensor. The loss of creatinine was found to be a first-order reaction with the activation energy of 64.7 kJ mol-1.

Microporous carbon for fast and simple electrochemical detection of imidacloprid insecticide in fruit and water samples.

Herein, a fast and sensitive electrochemical sensor was developed for imidacloprid detection using low-cost disposable microporous carbon screen-printed electrodes. The electrochemical behaviour of imidacloprid at the microporous material was investigated in detail. The developed sensor allowed imidacloprid detection in the linear range of 0.00-1.00 mM with a sensitivity of 14.43 ± 0.42 µA mM-1 and a detection limit of 2.54 µM (3s B/m). The sensor showed excellent selectivity and high tolerance to possible interference from other tested insecticides and ions. Excellent repeatability (3.42%, n = 3) and reproducibility (2.23%, n = 3) were demonstrated. Application of the sensor in various fruit and water samples without any treatment showed 96.2-103.0% recoveries. The developed sensor further revealed that the most effective method for removing imidacloprid residue from fruit samples was via washing with a mixture of 5% w/v NaCl and 5% w/v bicarbonate at 40 °C.

Microporous carbon in the selective electro-oxidation of molecular biomarkers: uric acid, ascorbic acid, and dopamine.

Herein, we demonstrate the superior electrocatalytic activities of microporous carbon in the oxidation of three molecular biomarkers, ascorbic acid (AA), dopamine (DA), and uric acid (UA), which are co-present in biological fluids. The voltammetric responses of AA, DA, and UA at the low-cost microporous carbon electrode show significantly better sensitivity and selectivity than other more expensive and commonly used electrode materials such as copper(ii) oxide, copper(i) oxide, and carbon nanotube. Differential pulse voltammetry at the microporous carbon electrode allows the detection of AA, DA, and UA with linear ranges of 100-2000 µM (AA), 10-150 µM (DA), and 10-150 µM (UA), sensitivities of 6.8 ± 0.2 nA µM-1 (AA), 261.4 ± 3.4 nA µM-1 (DA), and 93.5 ± 2.0 nA µM-1 (UA), and detection limits of 23.1 µM (AA), 0.2 µM (DA), and 1.7 µM (UA). The method has been validated with a synthetic urine sample to yield ∼100% recoveries for all three analytes. The developed method has been further applied in the investigation of the peroxide scavenging activity of UA.

Electrochemical oxidation of resorcinol: mechanistic insights from experimental and computational studies.

This work investigates the mechanisms of resorcinol oxidation by density functional theory (DFT) calculation and cyclic voltammetry measurements. Complementary data from experimental and computational studies provide new insights into the reaction mechanisms. At both macro- and micro-electrodes, cyclic voltammetry of resorcinol is chemically and electrochemically irreversible over the whole pH range (1-14). Resorcinol molecules undergo a 1H+ 1e- oxidation at pH < pK a1 and a 1e- oxidation at pH > pK a2 to form radicals. The radicals then readily react to form dimers/polymers deposited on the electrode surface. All of the experimental findings are consistent with the proposed mechanisms, including the apparent transfer coefficient (ß) of 0.6 ± 0.1, the slope of the peak potential (E p) against pH of -54 mV pH-1, the peak-shaped responses at micro-electrodes, and the fouling of the electrodes upon the oxidation of resorcinol. DFT calculation of the reaction energy of elementary steps and the eigenvalues of the highest occupied molecular orbital (HOMO) of the radical intermediates confirms that the (1H+) 1e- oxidation is the energetically favorable pathway. In addition to mechanistic insights, an electrochemical sensor is developed for resorcinol detection at microelectrodes in low ionic strength samples with the sensitivity of 123 ± 4 nA µM-1 and the limit of detection (3 sB m-1) of 0.03 µM.

Salivary glutathione in bipolar disorder: A pilot study.

BACKGROUND: Glutathione (GSH) is an important cellular antioxidant and its levels are decreased in some studies of bipolar patients. Saliva provides a simple and feasible means of measuring GSH but has not yet been applied to the study of bipolar disorder. The purpose of the study was to compare salivary levels of GSH and oxidized glutathione (GSSG) in bipolar patients and healthy controls. METHODS: Saliva was sampled from 22 medicated, euthymic patients with bipolar disorder and 20 healthy controls. GSH and GSSG were measured using an enzyme kinetic essay. RESULTS: GSH and GSSG were significantly higher in saliva from bipolar patients relative to controls. The ratio of GSH:GSSG was unchanged. There was no correlation between the measured clinical characteristics of the patients and GSH levels. LIMITATIONS: The main limitation of the study was the small sample size. Patients were medicated which may have influenced saliva production and hence GSH levels. In addition, salivary GSH may not reflect GSH status in tissues more directly involved in the pathophysiology of bipolar disorder. CONCLUSION: Salivary GSH can be readily measured in bipolar patients. Relative to controls, salivary levels of GSH and GSSG were increased in bipolar patients but their ratio was unchanged. The origin and significance of these change requires further study.

Coupled Optical and Electrochemical Probing of Silver Nanoparticle Destruction in a Reaction Layer.

The oxidation of silver nanoparticles is induced to occur near to, but not at, an electrode surface. This reaction at a distance from the electrode is studied through the use of dark-field microscopy, allowing individual nanoparticles and their reaction with the electrode product to be visualized. The oxidation product diffuses away from the electrode and oxidizes the nanoparticles in a reaction layer, resulting in their destruction. The kinetics of the silver nanoparticle solution-phase reaction is shown to control the length scale over which the nanoparticles react. In general, the new methodology offers a route by which nanoparticle reactivity can be studied close to an electrode surface.

Quantifying the Polymeric Capping of Nanoparticles with X-Ray Photoelectron Spectroscopy.

X-ray photoelectron spectroscopy was used to characterise silver nanoparticles capped with poly(ethylene) glycol (PEG) in a room-temperature ionic liquid (RTIL), 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF4 ]). The amounts of oxygen and silver present in nanoparticles capped with different molecular weight thiolated PEG chains were monitored, and the number of thiolated PEG chains per nanoparticle was calculated, an in situ characterisation not previously possible.

The fate of silver nanoparticles in authentic human saliva.

The physicochemical properties of silver nanoparticles (AgNPs) in human whole saliva are investigated herein. In authentic saliva samples, AgNPs exhibit a great stability with over 70% of the nanomaterial remaining intact after a 24-h incubation in the presence of ∼0.3 mM dissolved oxygen. The small loss of AgNPs from the saliva sample has been demonstrated to be a result of two processes: agglomeration/aggregation (not involving oxygen) and oxidative dissolution of AgNPs (assisted by oxygen). In authentic saliva, AgNPs are also shown to be more inert both chemically (silver oxidative dissolution) and electrochemically (electron transfer at an electrode) than in synthetic saliva or aqueous electrolytes. The results thus predict based on the chemical persistence (over a 24-h study) of AgNPs in saliva and hence the minimal release of hazardous Ag+ and reactive oxygen species that the AgNPs are less likely to cause serious harm to the oral cavity but this persistence may enable their transport to other environments.

Correction: Chemical analysis in saliva and the search for salivary biomarkers - a tutorial review.

Correction for 'Chemical analysis in saliva and the search for salivary biomarkers - a tutorial review' by Kamonwad Ngamchuea, et al., Analyst, 2018, 143, 81-99.

The mechanism of electrochemical reduction of hydrogen peroxide on silver nanoparticles.

The reduction of hydrogen peroxide on a silver nanoparticle modified boron doped diamond electrode in a neutral solution is shown to proceed through a CE mechanism. Hydrogen peroxide undergoes a disproportionation reaction to form oxygen (and water) on the silver surface, creating a diffusion layer of oxygen, which, at a sufficiently biased electrode, is then reduced to hydrogen peroxide. Voltammetry and a full mechanistic simulation are undertaken to confirm the mechanism, showing at short times a dependence of the reductive signal on waiting time prior to voltammetric analysis reflecting the extent of the disproportionation step which occurs prior to voltammetric analysis.

Martian Redox Chemistry: Oxygen Reduction in Low-Temperature Magnesium Perchlorate Brines.

NASA has a mandate to send humans to Mars by 2033. Recent discoveries regarding Mars include the likely presence of low-temperature liquid brines on the planet's surface. This work investigates redox chemistry in near saturated aqueous 2.8 M Mg(ClO4)2 at temperatures as low as -34 °C. These conditions are comparable to those thought to be found on the Martian surface. In particular, electro-reduction of oxygen is studied, and the diffusion coefficient and solubility of this important redox species are established.

Chemical analysis in saliva and the search for salivary biomarkers - a tutorial review.

Biomarkers refer to analytes that can be used in the diagnosis of diseases or disorders. In saliva, there are many components that are potential biomarkers, and increasing research has focussed on the development of saliva as a diagnostic fluid. This review summarizes the existing uses of salivary biomarkers and highlights the importance of the choice of saliva collection as well as the storage procedures. A case study on the effect of collection tools on the concentrations of one of the potential biomarkers, glutathione, is highlighted. Moreover, molecular diagnosis requires reliable measurement assays. This review presents electroanalytical methods for the detection of salivary biomarkers. It further reviews approaches that can be taken to improve the selectivity of electroanalytical assays without the use of biologically selective materials, notably without the use of enzymes or antibodies.

Dynamics of Silver Nanoparticles in Aqueous Solution in the Presence of Metal Ions.

Using a combined UV-vis, DLS, and electrochemical approach, this work experimentally studies the physical origin of the observed colorimetric sensitivity of aqueous silver nanoparticles toward divalent metal ions. In the presence of Pb2+, AgNPs are slow to reversibly form agglomerates (the time scale of the reverse deagglomeration process is of the order of hours). This agglomeration is shown to be induced by complex formation between Pb2+ and citrate groups localized on the AgNPs, reducing surface charges (zeta-potential) and hence electrostatic repulsion between the AgNPs. Other divalent metal ions including Ca2+, Cd2+, Zn2+, Ni2+, Co2+, and Sn2+ are also studied, and the resulting sizes of the AgNPs clusters and the extents of the UV-vis spectrum red-shift in λmax have a strong positive correlation with the metal-ligand (citrate) complex formation constant (Kf). This work thus serves as a guide for the selection of capping agents on the basis of Kf and demonstrates the correlation between sizes and spectrophotometric as well as electrochemical responses of the AgNPs clusters. Importantly, we give further physical insights into the size-dependent properties of AgNPs and emphasize the difference between theoretical and experimental values of extinction coefficients, where the latter is affected by the angle-dependent scattering intensities and the measurement technique used.

Single Oxidative Collision Events of Silver Nanoparticles: Understanding the Rate-Determining Chemistry.

The oxidative dissolution of citrate-capped silver nanoparticles (AgNPs, ∼50 nm diameter) is investigated herein by two electrochemical techniques: nano-impacts and anodic stripping voltammetry. Nano-impacts or single nanoparticle-electrode collisions allow the detection of individual nanoparticles. The technique offers an advantage over surface-immobilized methods such as anodic stripping voltammetry as it eliminates the effects of particle agglomeration/aggregation. The electrochemical studies are performed in different electrolytes (KNO3 , KCl, KBr and KI) at varied concentrations (≤20 mm). In nano-impact measurements, the AgNP undergoes complete oxidation upon impact at a suitably potentiostated electrode. The frequency of the nanoparticle-electrode collisions observed as current-transient spikes depends on the electrolyte identity, its concentration and the potential applied at the working electrode. The frequencies of the spikes are significantly higher in the presence of halide ions and increase with increasing potentials. From the frequency, the rate of AgNP oxidation as compared with the timescale the AgNP is in electrical contact with the electrode can be inferred, and hence is indicative of the relative kinetics of the oxidation process. Primarily based on these results, we propose the initial formation of the silver (I) nucleus (Ag+ , AgCl, AgBr or AgI) as the rate-determining process of silver oxidation on the nanoparticle.

Improving Single-Carbon-Nanotube-Electrode Contacts Using Molecular Electronics.

We report the use of an electroactive species, acetaminophen, to modify the electrical connection between a carbon nanotube (CNT) and an electrode. By applying a potential across two electrodes, some of the CNTs in solution occasionally contact the electrified interface and bridge between two electrodes. By observing a single CNT contact between two microbands of an interdigitated Au electrode in the presence and absence of acetaminophen, the role of the molecular species at the electronic junction is revealed. As compared with the pure CNT, the current magnitude of the acetaminophen-modified CNTs significantly increases with the applied potentials, indicating that the molecule species improves the junction properties probably via redox shuttling.