Electrochemical and X-ray Photoelectron Spectroscopy Surface Characterization of Interchain-Driven Self-Assembled Monolayer (SAM) Reorganization

Herein, we report a combined strategy encompassing electrochemical and X-ray photoelectron spectroscopy (XPS) experiments to investigate self-assembled monolayer (SAM) conformational reorganization onto an electrode surface due to the application of an electrical field. In particular, 3-mercaptopriopionic acid SAM (3MPA SAM) modified gold electrodes are activated with a 1-ethyl-3- (3-dimethylaminopropyl)carbodiimide (EDC) and N-hydroxysulfosuccinimide (NHSS) (EDC-NHSS) mixture by shortening the activation time, from 2 h to 15/20 min, labelled as Protocol-A, -B and -C, respectively. This step, later followed by a deactivation process with ethanolamine (EA), plays a key role in the reaction yields (formation of N-(2-hydroxyethyl)-3-mercaptopropanamide, NMPA) but also in the conformational rearrangement observed during the application of the electrical field. This study aims at explaining the high performance (i.e., single-molecule detection at a large electrode interface) of bioelectronic devices, where the 3MPA-based SAM structure is pivotal in achieving extremely high sensing performance levels due to its interchain interaction. Cyclic voltammetry (CV) experiments performed in K4Fe(CN)6:K3Fe(CN)6 for 3MPA SAMs that are activated/deactivated show similar trends of anodic peak current (IA) over time, mainly related to the presence of interchain hydrogen bonds, driving the conformational rearrangements (tightening of SAMs structure) while applying an electrical field. In addition, XPS analysis allows correlation of the deactivation yield with electrochemical data (conformational rearrangements), identifying the best protocol in terms of high reaction yield, mainly related to the shorter reaction time, and not triggering any side reactions. Finally, Protocol-C’s SAM surface coverage, determined by CV in H2SO4 and differential pulse voltammetry (DPV) in NaOH, was 1.29 * 1013 molecules cm2, being similar to the bioreceptor surface coverage in single-molecule detection at a large electrode interface

Bioelectrochemically Triggered Apoferritin-based Bionanoreactors:Synthesis of CdSe Nanoparticles and Monitoring with Leaky Waveguides

Herein, we describe a novel method for producing cadmium-selenide nanoparticles (CdSe NPs) with controlled size using apoferritin as a bionanoreactor triggered by local pH change at the electrode/solution interface. Apoferritin is known for its reversible self-assembly at alkaline pH. The pH change is induced electrochemically by reducing O2 through the application of sufficiently negative voltages and bioelectrochemically through O2 reduction catalyzed by laccase, co-immobilized with apoferritin on the electrode surface. Specifically, a Ti electrode is modified with (3-Aminopropyl)triethoxysilane, followed by glutaraldehyde cross-linking (1.5% v/v in H2O) of apoferritin (as the bionanoreactor) and laccase (as the local pH change triggering system). This proposed platform offers a universal approach to controlling the synthesis of semiconductor NPs within a bionanoreactor solely driven by (bio)electrochemical inputs. The CdSe NPs obtained through different synthetic approaches, namely electrochemical and bioelectrochemical, were characterized spectroscopically (UV-Vis, Raman, XRD) and morphologically (TEM). Finally, we conducted online monitoring of CdSe NPs formation within the apoferritin core by integrating the electrochemical system with LWs. The quantity of CdSe NPs produced through bioelectrochemical means was determined to be 2.08 ± 0.12 mg after 90 minutes of voltage application in the presence of O2. TEM measurements revealed that the bioelectrochemically synthesized CdSe NPs have a diameter of 4 ± 1 nm, accounting for 85% of the size distribution, a result corroborated by XRD data. Further research is needed to explore the synthesis of nanoparticles using different biological nanoreactors, as the process can be challenging due to the elevated buffer capacitance of biological media

Enzyme based field effect transistor: State‐of‐the‐art and future perspectives

Abstract The review discloses the historical and technological evolution of enzyme‐based field‐effect transistors (EnFETs) underlying the importance of gate electrode modification toward the implementation of novel FETs configurations such as extended‐gate FET (EG‐FETs) or EG organic FETs (EG‐OFETs). The working principle of the EnFETs as postulated by Bergveld in 1970, who defined the EnFET as an ion‐selective FET (ISFET) modified with enzyme‐membrane, is also discussed considering the analytical equations related to the EnFET output response. For each category, namely EnFETs, EG‐FETs, and EG‐OFETs, we reviewed the key devices’ configurations that addressed the research in this field in the last 40 years with particular attention to the analytical figures of merit