RESUMO
In this study, Au-NiFe2O4 hetero-nanostructures (Au-NFO HNs) have been successfully developed and proposed as an efficient photoactive material for the construction of a photoelectrochemical sensor for the detection of paracetamol (PCM) under visible light irradiation. When Au NPs were in intimate contact with NFO NFs, a built-in electric field and Schottky barrier at the NFO/Au interface were established and downward band bending occurred. By using monochromatic 532 nm laser excitation, the photo-generated electrons on the NFO conduction band were promptly migrated to the Au Fermi level due to the presence of a built-in electric field and downward band bending, and together with the hot electrons induced by localized surface plasmon resonance characteristics of Au NPs could concurrently contribute to the enhanced photoelectrochemical activity. Furthermore, the Schottky barrier prevents the transfer of photo-generated holes from the valence band of NFO to Au, thereby suppressing the recombination of photo-generated electron-hole pairs and prolonging charge carrier lifetimes. A series of electrochemical kinetic parameters were determined and the results showed that in the presence of visible light irradiation, the interfacial charge transfer ability, electrocatalytic activity, and adsorption/diffusion capacity of Au-NFO HNs-modified electrode were remarkably enhanced compared to the dark environment. As a result, the photoelectrochemical sensing platform based on Au-NFO HNs showed noteworthy analytical performance towards PCM detection in the wide linear ranges from 0.5-200 µM, high electrochemical sensitivity of 1.089 µA µM-1 cm-2, and low detection limit of 0.38 µM. Furthermore, the repeatability, anti-interference ability, and feasibility of the proposed photoelectrochemical sensor were also evaluated. This study will establish a more comprehensive understanding and promote ongoing interest in constructing advanced and efficient plasmonic metal/semiconductor hetero-nanostructures for analytical photoelectrochemistry.
RESUMO
In this study, we demonstrate the influence of crystallinity and morphology on the analytical performance of various Cu2MoS4 (CMS) nanocatalysts-based electrochemical sensors for the high-efficiency detection of Ofloxacin (OFX) antibiotic. The electrochemical kinetics parameters including peak current response (ΔIp), peak-to-peak separation (ΔEp), electrochemically active surface area (ECSA), electron-transfer resistance (Rct), were obtained through the electrochemical analyses, which indicate the single-crystalline nature of CMS nanomaterials (NMs) is beneficial for enhanced electron-transfer kinetics. The morphological features and the electrochemical results for OFX detection substantiate that by tuning the tube-like to plate-like structures of the CMS NMs, it might noticeably enhance multiple adsorption sites and more intrinsic active catalytic sites due to the diffusion of analytes into the interstitial spaces between CMS nanoplates. As results, highly single-crystalline and plate-shaped morphology structures of CMS NMs would significantly enhance the electrocatalytic OFX oxidation in terms of onset potential (Eonset), Tafel slope, catalytic rate constant (kcat), and adsorption capacity (Γ). The CMS NMs-based electrochemical sensing platform showed excellent analytical performance toward the OFX detection with two ultra-wide linear detection concentration ranges from 0.25-100 and 100-1000â µM, a low detection limit of 0.058â µM, and an excellent electrochemical sensitivity (0.743â µA µM-1 cm-2).
RESUMO
In this study, crystalline spinel zinc ferrite nanoparticles (ZnFe2O4 NPs) were successfully prepared and proposed as a high-performance electrode material for the construction of an electrochemical sensing platform for the detection of paracetamol (PCM). By modifying a screen-printed carbon electrode (SPE) with ZnFe2O4 NPs, the electrochemical characteristics of the ZnFe2O4/SPE and the electrochemical oxidation of PCM were investigated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), chronoamperometry (CA), and differential pulse voltammetry (DPV) methods. The calculated electrochemical kinetic parameters from these techniques including electrochemically active surface area (ECSA), peak-to-peak separation (ΔEp), charge transfer resistance (Rct), standard heterogeneous electron-transfer rate constants (k0), electron transfer coefficient (α), catalytic rate constant (kcat), adsorption capacity (Γ), and diffusion coefficient (D) proved that the as-synthesized ZnFe2O4 NPs have rapid electron/mass transfer characteristics, intrinsic electrocatalytic activity, and facilitate the adsorption-diffusion of PCM molecules towards the modified electrode surface. As expected, the ZnFe2O4/SPE offered excellent analytical performance towards sensing of PCM with a detection limit of 0.29 µM, a wide linear range of 0.5-400 µM, and high electrochemical sensitivity of 1.1 µA µM-1 cm-2. Moreover, the proposed ZnFe2O4-based electrochemical nanosensor also exhibited good repeatability, high anti-interference ability, and practical feasibility toward PCM sensing in a pharmaceutical tablet. Based on these observations, the designed electrochemical platform not only provides a high-performance nanosensor for the rapid and highly efficient detection of PCM but also opens a new avenue for routine quality control analysis of pharmaceutical formulations.
RESUMO
Despite the utilization of external magnetic field (MF) in promoting the intrinsic unique features of magnetic nanomaterials in many different applications has been reported, however the origin of MF-dependent electrochemical behaviors as well as the electrochemical response of analytes at the electrode in sensor applications is still not clear. In this report, the influence of MF on the electrolyte's physicochemical properties (polarization, mass transport, charge/electron transfer) and electrode's properties (conductivity, morphology, surface area, interaction, adsorption capability, electrocatalytic ability) was thoroughly investigated. Herein, the working electrode surface was modified with carbon spheres (CSs), magnetic nanoparticles (Fe3O4NPs), and their nanocomposites (Fe3O4@CSs), respectively. Then, they were directly used to enhance the electrochemical characteristics and response-ability of chloramphenicol (CAP). More interestingly, a series of various kinetic parameters related to the diffusion-controlled process of K3[Fe(CN)6]/K4[Fe(CN)6)] and the adsorption-controlled process of CAP were calculated at the bare electrode and the modified electrodes with and without the presence of MF. These parameters not only exhibit the crucial role of the modification of electrode surface with the proposed materials but also show positive impacts of the presence of external MF. Besides, the mechanism and hypothesis for the enhancements were proposed and discussed in detail, further demonstrating the development potential of using Fe3O4@CS nanocomposites with MF assistant for advanced energy, environmental, and sensor related-applications.
Assuntos
Carbono , Cloranfenicol , Carbono/química , Técnicas Eletroquímicas , Eletrodos , Eletrólitos , Campos MagnéticosRESUMO
Modern society has been facing serious health-related problems including food safety, diseases and illness. Hence, it is urgent to develop analysis methods for the detection and control of food contaminants, disease biomarkers and pathogens. As the traditional instrumental methods have several disadvantages, including being time consuming, and having high cost and laborious procedures, optical nanosensors have emerged as promising alternative or complementary approaches to those traditional ones. With the advantages of simple preparation, high surface-to-volume ratio, excellent biocompatibility, and especially, unique optical properties, gold nanoparticles (AuNPs) have been demonstrated as excellent transducers for optical sensing systems. Herein, we provide an overview of the synthesis of AuNPs and their excellent optical properties that are ideal for the development of optical nanosensors based on local surface plasmon resonance (LSPR), colorimetry, fluorescence resonance energy transfer (FRET), and surface-enhanced Raman scattering (SERS) phenomena. We also review the sensing strategies and their mechanisms, as well as summarizing the recent advances in the monitoring of food contaminants, disease biomarkers and pathogens using developed AuNP-based optical nanosensors in the past seven years (2015-now). Furthermore, trends and challenges in the application of these nanosensors in the determination of those analytes are discussed to suggest possible directions for future developments.
RESUMO
The rational design of nanomaterials for electrochemical nanosensors from the perspective of structure-property-performance relationships is a key factor in improving the analytical performance toward residual antibiotics in food. We have investigated the effects of the crystalline phase and copper loading amount on the detection performance of Cu-MoS2 nanocomposite-based electrochemical sensors for the antibiotic chloramphenicol (CAP). The phase composition and copper loading amount on the MoS2 nanosheets can be controlled using a facile electrochemical method. Cu and Cu2O nanoparticle-based electrochemical sensors showed a higher CAP electrochemical sensing performance as compared to CuO nanoparticles due to their higher electrocatalytic activity and conductivity. Moreover, the design of Cu-MoS2 nanocomposites with appropriate copper loading amounts could significantly improve their electrochemical responses for CAP. Under optimized conditions, Cu-MoS2 nanocomposite-based electrochemical nanosensor showed a remarkable sensing performance for CAP with an electrochemical sensitivity of 1.74 µA µM-1 cm-2 and a detection limit of 0.19 µM in the detection range from 0.5-50 µM. These findings provide deeper insight into the effects of nanoelectrode designs on the analytical performance of electrochemical nanosensors.
RESUMO
In this study, manganese ferrite-graphene oxide (MFO-GO) nanocomposites were prepared via a co-precipitation reaction of Fe3+ and Mn2+ ions in a GO suspension. The effects of graphene oxide on the physicochemical characteristics, magnetic properties and adsorption activities of the MFO-GO nanocomposites were studied. Methylene blue (MB) and arsenic(v) were used in this study as model water pollutants. With an increase in the GO content in the range of 10 wt% to 50 wt%, the removal efficiency for both MB dye and arsenic(v) ions was improved. Our adsorption data revealed that the adsorption behavior of MB dye showed good agreement with the Langmuir isotherm model and pseudo-second-order equation, whereas the Freundlich isotherm model was more suitable for simulating the adsorption process of arsenic(v) ions on the MFO-GO nanocomposites. In addition, an important role of the GO content in the adsorption mechanisms of both MB dye and arsenic(v) ions was found, in which GO nanosheets play a key role in the mechanisms of electrostatic/ionic interactions, oxygen-containing groups and π-π conjugation in the case of the adsorption of MB dye, whereas the role of the GO content is mainly related to the mechanism of electrostatic/ionic interactions in the case of the adsorption of arsenic(v). Graphene oxide has the functions of increasing the number of active binding sites comprising oxygen-containing functional groups, reducing the agglomeration of MFO nanoparticles, increasing the number of adsorption sites, and improving the electrostatic/ionic interactions between adsorbents and adsorbates in order to enhance the adsorption performance of cationic organic dyes and/or heavy metal anions from aqueous solutions.