Abstract
Over the years, literature reported inumerous applications of electrochemical and surface plasmon resonance (SPR) immunoassays for biosensing but, so far, the combination of the two methods in the same sensing spot for analytical purposes is much less explored and discussed. The aim of this Review is to highlight the great potential of electrochemistry combined-SPR (eSPR) as analytical tool for screening chemically and biologically relevant (bio)molecules by combining the unique features of SPR integrated with electrochemical readout.In the first part of the Review, we describe the urgent need of innovative methods for screening clinical biological markers (General Introduction), briefly discuss general concepts of SPR and electrochemical sensing (Concepts behind eSPR biosensors) and highlight the hyphenation of two methods to developed combined biosensing systems (Set-up configuration and eSPR principles). Firstly, we briefly give an overview of the setup for implementation of eSPR technique and discuss some relevant experimental conditions to perform the combined optical and electrochemical measurements. Then, the principles and fundamentals of eSPR biosensors are presented and described. We also present representative examples of eSPR biosensors in the literature (Applications of eSPR biosensors).In the second part, we review studies on how combined electrical and plasmonic detection contributed to the biosensing field, in particular, for the successful screening of clinically relevant biomolecules, namely proteins (Detection of proteins), nucleic acids (Detection of nucleic acids), small size chemical species (Detection of small molecules) and cells (Living-cell Analysis).Finally, we discuss the current limitations of eSPR biosensors performance and suggest possible ways to overcome these limitations (Limitations and optimization) and then we explore aspects about the development of the method and its applications and discuss areas of likely future growth (Conclusions and perspectives). (c) 2022 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Abstract
In this work, we describe an innovative methodology based on combined surface plasmon resonance (SPR) and electrochemical responses (eSPR) in the same immunoassay for screening CA 15-3 cancer biomarker with high sensitivity (and selectivity), in a very simple, label-free, accurate, and fully automated manner. Detection was achieved by performing two simple steps. In the first step, direct SPR was used to monitor CA 15-3 interaction with surface immobilized antibody. Two linear response ranges were obtained and the detection limit achieved is poor (LOD of 21 U mL(-1)). However, in the second detection step, electrochemical measurements at the SPR gold surface were performed to measure the decrease of redox probe peak current upon antigen-antibody interaction, providing a suitable amplification strategy to lower detection levels of CA 15-3 (LOD of 0.0998 U mL(-1)), without the need of additional complex and/or expensive amplification steps to enhance the sensitivity. Moreover, selectivity studies were performed against other common cancer biomarkers and the results showed that the eSPR immunosensor is selective for the CA 15-3 protein. Finally, the clinical applicability of the developed eSPR biosensing methodology was successfully applied to detect CA 15-3 in human serum samples at clinically relevant levels due to the high sensitivity of electrochemical readout. The same concept may be further extended to other proteins of interest.

Abstract
In this work, we report for the first time the accumulation activity by energized rat heart mitochondria and the ionic transfer process at a liquid liquid interface of a novel mitochondria-targeted antioxidant, named as AntiOxCIN(4), which is structurally based on a hydroxycinnamic acid. Lipophilicity studies conducted at the water/1,6-dichlorohexane (DCH) interface allowed the building up of an ionic partition diagram of AntiOxCIN(4) in accordance with the electrochemical data obtained. The partition coefficients of both positively charged (-2.3) and zwitterionic (0.2) forms of the antioxidant were determined. This study contributed to gaining an insight about the ability of the synthesized antioxidants to cross biomembrane barriers by using an interface between two immiscible electrolyte solutions (ITIES) as a model system.

Abstract
In this work, we combined electrochemical techniques with SPR (eSPR) for the label-free detection of cancer biomarker miRNA-145. Detection was performed in a simple two-step assay. In the first step, the gold sensor surface, previously functionalized with a self-assembled monolayer (SAM) of thiolated RNA probes is incubated with the sample containing the target RNA biomarker. In this step, hybridization of RNA fragments with complementary immobilized probes was monitored in real-time by SPR. In the second step, eSPR measurements were performed to improve the sensitivity of the hybridization assay. Potential-induced deposition of a redox probe at the sensor surface resulted in enhanced SPR response promoted by the electrochemical process, thereby allowing the detection of miRNA-145 at femtomolar level (LOD = 0.56 fM), without sample derivatization or post-hybridization treatment for signal amplification. Good linearity was achieved (R-2 = 0.984) over the concentration range from 1.0 fM and 10 nM. Furthermore, the developed eSPR biosensor showed high selectivity towards single-base and two-base mismatch sequences and detection of target miRNA-145 in synthetic human serum was successful achieved.

Abstract
In this work, electrically-conducting poly(Toludine Blue) was employed for the first time as synthetic receptor film, prepared by Molecular Imprinting strategies and using electrochemical methods, for the specific screening of breast cancer biomarker Carbohydrate Antigen 15.3 (CA 15-3). The protein imprinted poly(Toluidine Blue) film was grown in a pre-formed Toluidine Blue (TB) tailed SAM at the AuSPE surface, which greatly enhanced the stability against degradation of the Molecular Imprinted Polymer (MIP) film at the electrode surface. The MIP receptor film recognition ability towards the protein was investigated by fitting data to Freundlich isotherm. The binding affinity (K-p) obtained for the MIP system was significantly higher (similar to 12-fold) to that obtained for the NIP system, demonstrating the success of the approach in creating imprinted materials that specifically respond to CA 15-3 protein. The incubation of the MIP modified electrode with increasing concentration of protein (from 0.10 U mL(-1) to 1000 U mL(-1)) resulted in a decrease of the ferro/ferricyanide redox current. The device displayed linear response from 0.10 U mL(-1) to 100 U mL(-1) and LODs below 0.10 U mL(-1) were obtained from calibration curves built in neutral buffer and diluted artificial serum, using DPV technique, enabling the detection of the protein biomarker at clinically relevant levels. The developed MIP biosensor was applied to the determination of CA 15-3 in spiked serum samples with satisfactory results. The developed device provides a new strategy for sensitive, rapid, simple and cost-effective screening of CA 15-3 biomarker. Importantly, the overall approach seems suitable for point-of-care (PoC) use in clinical context.

Abstract
Zinc oxide is widely used in the manufacture of a vast number of consumer goods and industrial applications. The employ of nano and sub-micrometer zinc oxide materials has recently been introduced as a more economic and more effective alternative to bulk zinc oxide. Furthermore zinc oxide is being used as antibacterial material since metal oxides are recognized as possessing antibacterial properties and are regarded as safe materials to human beings and animals. The present work aims to present our study on the antibacterial properties of zinc oxide particles prepared by a polyol thermal method. Spherical submicrometer ZnO particles were prepared and their antibacterial properties were tested in aqueous suspensions of E. coli bacteria. For ZnO concentrations higher than 50 ppm an inhibition of the growth rate of bacteria higher than 95 % is achieved.