The electroanalytical field has exploited great advantages in using paper-based substrates, even if the word "paper" might be general. In fact, the mainly adopted paper-based substrates are often chromatographic and office ones. They are characterized by the following main features (and drawbacks): chromatographic paper is well-established for storing reagents/ treating samples, but the sensitivity compared to traditional screen-printed ones is lower (due to porosity), while office paper represents a sustainable alternative to plastic (with similar sensitivity), but its porosity is not enough to load reagents. To overcome the limitations that might arise due to the adoption of a type of individual paper-based substrate, herein, we describe for the first time the development of a two-dimensional merged paper-based device for electrochemical copper ion detection in serum. In this work, we report a novel configuration to produce an integrated all-in-one electrochemical device, in which no additional working medium has to be added by the end user and the sensitivity can be tuned by rapid preconcentration on porous paper, with the advantage of making the platform adaptable to real matrix scenarios. The novel architecture has been obtained by combining office paper to screen-print a sustainable and robust electrochemical strip and a chromatographic disk to (1) store the reagents, (2) collect real samples, and (3) preconcentrate the analyte of interest. The novel sensing platform has allowed us to obtain a detection limit for copper ions down to 4 ppb in all the solutions that have been investigated, namely, standard solutions and serum, and a repeatability of ca. 10% has been obtained. Inductively coupled plasma-mass spectrometry measurements confirmed the satisfactory correlation.
MicroRNAs (miRNAs) are clinical biomarkers for various human diseases, including cancer. They have been found in liquid biopsy samples, including various bodily fluids. They often play an important role in the early diagnosis and prognosis of cancer, and the development of simple and effective analytical methods would be of pivotal importance for the entire community. The determination of these targets may be affected by the different physicochemical parameters of the specimen of interest. In this work, an electrochemical detection platform for miRNA based on a screen-printed gold electrode was developed. In the present study, miRNA-21 was selected as a model sequence, due to its role in prostate, breast, colon, pancreatic, and liver cancers. A DNA sequence modified with methylene blue (MB) was covalently bound to the electrochemical strip and used to detect the selected target miRNA-21. After optimization of selected parameters in standard solutions, including the study of the effect of pH, the presence of interferent species, and NaCl salt concentration in the background, the application of square-wave voltammetry (SWV) technique allowed the detection of miRNA-21 down to a limit in the order of 2 nM. The developed device was then applied to several urine samples. In this case too, the device showed high selectivity in the presence of the complex matrix, satisfactory repeatability, and a limit of detection in the order of magnitude of nM, similarly as what observed in standard solutions.
Although heavy metals represent a major threat for ecosystem and human health, reference methods for their monitoring are characterized by time-consuming procedures, skilled personnel and sophisticated equipment (e.g. ICP-MS, AAS). Here, an electrochemical strip for the determination of lead and cadmium in clinical, environmental, and food matrices has been developed. The Bismuth film-based flexible device has been optimized and it has been able to detect cadmium and lead, respectively, down to at detection limit of 1.3 and 2 ppb. The use of Whatman No.1 chromatographic paper has allowed the improvement of the sensitivity towards the detection of heavy metals because of the porosity that allowed to pre-concentrate species. This led to an improvement in the sensitivity, with a detection limit of 0.3 and 0.5 ppb, respectively, to cadmium and lead, and offers the possibility to tune the sensitivity according to needs, e.g., improving the number of pre-concentration steps. Subsequently, the application of the electrochemical sensor in drinking water, mussel, and blood serum was evaluated, demonstrating how these hybrid polyester-paper electrochemical strips can significantly lower the time and costs for on-site measurements, through analytical methods of simple use. The accuracy has been evaluated by comparison with ICP-MS measurements.
The adoption of electrochemical principles to realize on-field analytical tools for detecting pollutants represents a great possibility for food safety and environmental applications. With respect to the existing transduction mechanisms, i.e., colorimetric, fluorescence, piezoelectric etc., electrochemical mechanisms offer the tremendous advantage of being easily miniaturized, connected with low cost (commercially available) readers and unaffected by the color/turbidity of real matrices. In particular, their versatility represents a powerful approach for detecting traces of emerging pollutants such as cyanotoxins. The combination of electrochemical platforms with nanomaterials, synthetic receptors and microfabrication makes electroanalysis a strong starting point towards decentralized monitoring of toxins in diverse matrices. This review gives an overview of the electrochemical biosensors that have been developed to detect four common cyanotoxins, namely microcystin-LR, anatoxin-a, saxitoxin and cylindrospermopsin. The manuscript provides the readers a quick guide to understand the main electrochemical platforms that have been realized so far, and the presence of a comprehensive table provides a perspective at a glance.
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