The control of acidity drives the assembly of biopolymers that are essential for a wide range of applications. Its miniaturization can increase the speed and the possibilities of combinatorial throughput for their manipulation, similar to the way that the miniaturization of transistors allows logical operations in microelectronics with a high throughput. Here, we present a device containing multiplexed microreactors, each one enabling independent electrochemical control of acidity in similar to 2.5 nL volumes, with a large acidity range from pH 3 to 7 and an accuracy of at least 0.4 pH units. The attained pH within each microreactor (with footprints of similar to 0.3 mm2 for each spot) was kept constant for long retention times (similar to 10 min) and over repeated cycles of >100. The acidity is driven by redox proton exchange reactions, which can be driven at different rates influencing the efficiency of the device in order to achieve more charge exchange (larger acidity range) or better reversibility. The achieved performance in acidity control, miniaturization, and the possibility to multiplex paves the way for the control of combinatorial chemistry through pH-and acidity controlled reactions.

In this work, we present the introductory methodology for a graphene field-effect transistor (GFET)-based platform for probing the electrochemical fingerprints of amino acids, designed to enable stable and controlled surface chemistry and electrochemical measurements toward peptide and protein sequencing. We begin with a focused conceptual review that motivates electrochemical fingerprinting as a strategy for amino acid and peptide identification and contextualizes this approach within recent advances in protein manipulation relevant to sequencing. We then describe a graphene functionalization protocol that facilitates the directional attachment of amino acids onto the graphene surface. This surface chemistry is quantitatively characterized through surface plasmon resonance (SPR), yielding surface densities in the order of 10¹² molecules/cm². The same functionalization protocol enables in situ peptide synthesis directly on graphene, as demonstrated by the successful synthesis of a model tripeptide. To support electrochemical interrogation, we developed three complementary platforms for sensor preconditioning, surface functionalization, and titration-based electrochemical measurements, compatible with both aqueous and organic solutions. Preliminary stability measurements indicate a Dirac point drift below 10 mV over 45 min. Altogether, this work establishes the experimental foundations for electrochemical amino acid and peptide fingerprinting using GFET sensors and provides a framework for the future development of electrochemically enabled protein sequencing technologies.

Sensors to monitor the immune status of an individual play a crucial role in understanding the acquired immunity or signs of a latent infection. Such sensors can be an effective tool to manage infection and to design treatment options in vulnerable populations. We demonstrate here highly sensitive detection of acquired immunity to Cytomegalovirus CMV by detection of anti-CMV antibodies using plasmon-enhanced fluorescence (PEF). The PEF sensors leverage plasmonic enhancement from a high density of intense electromagnetic hotspots in self-assembly-derived gold nanopillar arrays. Comparing PEF assays with assays on a planar surface plasmon resonance sensor shows the PEF sensors to be sensitive to a small fraction of the antibodies on the surface. The detection scheme deploys peptide monolayers with specific affinity to anti-CMV antibodies to capture them onto the sensor surfaces. The results of the assay on the PEF sensor reveal high promise for sensors with miniaturized sensing footprints, ease of spatial multiplexing, high sensitivity, and quick response times. The developments are readily applicable to a range of other diagnostic contexts where peptide–protein interactions and self-assembly-derived PEF sensors can be leveraged.

Correction for ‘Universal control of proton concentration using an electrochemically generated acid compatible with miniaturization’ by Janwa El-Maiss et al., Nanoscale Adv., 2022, 4, 3233–3242, https://doi.org/10.1039/D2NA00275B.

The drive to miniaturize sensing footprints to the micro- and nanoscale has been motivated by reduced sensor real estate, lower sample consumption, and quick response times. However, there remains a limited understanding of how reducing sensor active areas impacts analyte–sensor interactions at fixed analyte concentrations. Using gold nanoparticles as a model analyte, we demonstrate that diminishing sensor active areas are associated with a nonlinear enhancement of analyte surface densities without changing the solution concentration. This behavior is rationalized by correlating the reduced sensor dimensions to an increase in the “effective” analyte availability per surface site. Consequently, sensors with reduced footprints would require substantially fewer analyte molecules to achieve surface densities comparable to those of macroscopic sensors. The resulting increase in nanoparticle surface density further translates into enhanced signal intensities in surface-enhanced Raman detection, arising from the higher density of nanoparticle–substrate plasmonic hotspots within a fixed optical measurement footprint. Overall, the work highlights how micro- and nanoscale sensors with active areas approaching the dimensions of the measurement footprint of highly sensitive transducers (e.g., nanowires or plasmonic hotspots) maximize the benefits of sensor miniaturization.

Electrolyte degradation and trace water contamination critically affect the lifetime and safety of lithium-ion batteries. In organic-based electrolytes such as acetonitrile (MeCN), even small amounts of water can trigger ${\mathrm{PF}}_6^{-}$ hydrolysis, producing HF, POF₃, and related species that contribute to electrolyte ageing and alter interfacial reactions. This study explores the electrochemical signatures of ageing and moisture contamination in Bu₄NPF₆- and LiPF₆-based MeCN electrolytes through a systematic cyclic voltammetry protocol. Platinum electrodes with different surface morphologies—flat, Nafion-coated, and nanostructured—were compared to assess their sensitivity to water-induced degradation. Cathodic Faradaic currents appearing around −0.7 to −1.0 V vs. Ag/AgCl were attributed to the protonic species generated by ${\mathrm{PF}}_6^{-}$-induced hydrolysis. The presence of LiPF₆, commonly used in battery electrolytes, further increases the concentration of anions responsible for the protonic species, therefore contributing to the acceleration of the electrolyte degradation. Experiments using a Nafion proton-conductive membrane assess the protonic origin of these peaks. Meanwhile, nanostructured platinum exhibits approximately four times higher current responses and enhanced sensitivity to water additions, reflecting the influence of surface roughness and active area. Overall, the findings indicate that electrode morphology significantly influences the detectability of ageing- and water-driven reactions, supporting the potential of nanostructured Pt as a diagnostic material for in situ monitoring.