skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Supersensitive CeO x -based nanocomposite sensor for the electrochemical detection of hydroxyl free radicals
It is well known that an excess of hydroxyl radicals (˙OH) in the human body is responsible for oxidative stress-related diseases. An understanding of the relationship between the concentration of ˙OH and those diseases could contribute to better diagnosis and prevention. Here we present a supersensitive nanosensor integrated with an electrochemical method to measure the concentration of ˙OH in vitro. The electrochemical sensor consists of a composite comprised of ultrasmall cerium oxide nanoclusters (<2 nm) grafted to a highly conductive carbon deposited on a screen-printed carbon electrode (SPCE). Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were used to analyze the interaction between cerium oxide nanoclusters and ˙OH. The CV results demonstrated that this electrochemical sensor had the capacity of detecting ˙OH with a high degree of accuracy and selectivity, achieving a consistent performance. Additionally, EIS results confirmed that our electrochemical sensor was able to differentiate ˙OH from hydrogen peroxide (H 2 O 2 ), which is another common reactive oxygen species (ROS) found in the human body. The limit of detection (LOD) observed with this electrochemical sensor was of 0.6 μM. Furthermore, this nanosized cerium oxide-based electrochemical sensor successfully detected in vitro the presence of ˙OH in preosteoblast cells from newborn mouse bone tissue. The supersensitive electrochemical sensor is expected to be beneficially used in multiple applications, including medical diagnosis, fuel–cell technology, and food and cosmetic industries.  more » « less
Award ID(s):
1817294
PAR ID:
10230829
Author(s) / Creator(s):
; ; ; ; ;
Date Published:
Journal Name:
Nanoscale
Volume:
13
Issue:
9
ISSN:
2040-3364
Page Range / eLocation ID:
5136 to 5144
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract Hydroxyl radicals (•OH) are well known as crucial chemicals for maintaining the normal activities of human cells; however, the excessive concentration of •OH disrupts their normal function, causing various diseases, including liver and heart diseases, cancers, and neurological disorders. The detection of •OH as a biomarker is thus essential for the early diagnosis of these serious conditions. Herein, a novel electrochemical sensor comprising a composite of cerium oxide nanoclusters, gold nanoparticles, and a highly conductive carbon was developed for detecting •OH. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were employed to characterize the signals generated by the interaction of the composite with •OH radicals. The CV results revealed that the developed sensor could accurately and selectively detect •OH in the Fenton reaction. The sensor demonstrated a linear relationship between the current peak and •OH concentration in the range 0.05 - 0.5 mM and 0.5 - 5 mM with a limit of detection (LOD) of 58 µM. In addition, EIS studies indicated that this electrochemical sensor could distinguish between •OH and similar reactive oxygen species (ROS), like hydrogen peroxide (H2O2). It is also worth mentioning that additional merits, such as reproducibility, repeatability, and stability of the sensor were confirmed. 
    more » « less
  2. Hydroxyl radicals (•OH) are known as essential chemicals for cells to maintain their normal functions and defensive responses. However, a high concentration of •OH may cause oxidative stress-related diseases, such as cancer, inflammation, and cardiovascular disorders. Therefore, •OH can be used as a biomarker to detect the onset of these disorders at an early stage. Reduced glutathione (GSH), a well-known tripeptide for its antioxidant capacity against reactive oxygen species (ROS), was immobilized on a screen-printed carbon electrode (SPCE) to develop a real-time detection sensor with a high selectivity towards •OH. The signals produced by the interaction of the GSH-modified sensor and •OH were characterized using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The CV curve of the GSH-modified sensor in the Fenton reagent exhibited a pair of well-defined peaks, demonstrating the redox reaction of the electrochemical sensor and •OH. The sensor showed a linear relationship between the redox response and the concentration of •OH with a limit of detection (LOD) of 49 µM. Furthermore, using EIS studies, the proposed sensor demonstrated the capability of differentiating •OH from hydrogen peroxide (H2O2), a similar oxidizing chemical. After being immersed in the Fenton solution for 1 hr, redox peaks in the CV curve of the GSH-modified electrode disappeared, revealing that the immobilized GSH on the electrode was oxidized and turned to glutathione disulfide (GSSG). However, it was demonstrated that the oxidized GSH surface could be reversed back to the reduced state by reacting with a solution of glutathione reductase (GR) and nicotinamide adenine dinucleotide phosphate (NADPH), and possibly reused for •OH detection. 
    more » « less
  3. A glucose biofuel cell on a flexible bacterial nanocellulose film was prepared. The bioelectrodes were printed using gold ink as the conductive material. The anode was modified with colloidal platinum for the oxidation of glucose. The cathode was modified with a nanocomposite comprising gold nanoparticles (AuNPs) and silver oxide (Ag2O) nanoparticles. The cathode was characterized via cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and UV spectroscopy techniques. The assembled biofuel cell generated a maximum open circuit voltage (V oc ) of 0.485 V, short circuit current (I sc ) of 0.352 mA/cm 2 , and a maximum peak power density (P max ) of 0.032 mW/cm 2 when operating in 30 mM concentration. This system showed a stable and linear performance with a linear range of 1 mM to 30 mM glucose. The gold printed electrode process is applicable to the development of wearable and implantable abiotic biofuel cell. 
    more » « less
  4. null (Ed.)
    Reactive oxygen species (ROS) have been found in plants, mammals, and natural environmental processes. The presence of ROS in mammals has been linked to the development of severe diseases, such as diabetes, cancer, tumors, and several neurodegenerative conditions. The most common ROS involved in human health are superoxide (O2•−), hydrogen peroxide (H2O2), and hydroxyl radicals (•OH). Organic and inorganic molecules have been integrated with various methods to detect and monitor ROS for understanding the effect of their presence and concentration on diseases caused by oxidative stress. Among several techniques, fluorescence and electrochemical methods have been recently developed and employed for the detection of ROS. This literature review intends to critically discuss the development of these techniques to date, as well as their application for in vitro and in vivo ROS detection regarding free-radical-related diseases. Moreover, important insights into and further steps for using fluorescence and electrochemical methods in the detection of ROS are presented. 
    more » « less
  5. Continuous greenhouse gas monitoring at sub-zero temperatures is needed for monitoring greenhouse gas emission in cold environments such as the Arctic tundra. This work reports a single-frequency electrochemical impedance sensing (SF-EIS) method for real-time continuous monitoring of carbon dioxide (CO2) at a wide range of temperatures (−15 to 40 °C) by using robust ionic liquid (IL) sensing materials and noninvasive, low-power, and low-cost impedance readout mechanisms since they cause minimal changes in the sensing interface, avoiding the baseline change for long-term continuous sensing. In addition, a miniaturized planar electrochemical sensor was fabricated that incorporates a hydrophobic 1-butyl-1-methylpyrrolidinium bis(trifluromethylsulfonyl)imide ([Bmpy][NTf2]) IL electrolyte and Pt black electrode materials. The high viscosity of the ILs facilitates the formation of thin, ordered, and concentrated layers of ionic charges, and the inverse relationship of IL viscosity with temperature makes them especially suited for impedance sensing at low temperatures. The unique low-temperature properties of ILs together with EIS transduction mechanisms are shown to be sensitive and selective for continuously monitoring CO2 at a −15 to 40 °C temperature range via impedance changes at a specifically selected frequency at the open circuit potential (OCP). Molecular dynamics simulations revealed insights into the structure and dynamics of the IL at varying temperatures in the presence of methane and CO2 and provided potential explanations for the observed sensing results. The miniaturized and flexible planar electrochemical sensor with the [Bmpy][NTf2] electrolyte was tested repeatedly at subzero temperatures over a 58-day period, during which good stability and repeatability were obtained. The CO2 impedance sensor was further tested for sensing CO2 from soil samples and shows promising results for their use in real-time monitoring of greenhouse gas emissions in cold temperatures such as permafrost soils. 
    more » « less