RESUMEN
Electrochemical research often requires stringent combinations of experimental parameters that are demanding to manually locate. Recent advances in automated instrumentation and machine-learning algorithms unlock the possibility for accelerated studies of electrochemical fundamentals via high-throughput, online decision-making. Here we report an autonomous electrochemical platform that implements an adaptive, closed-loop workflow for mechanistic investigation of molecular electrochemistry. As a proof-of-concept, this platform autonomously identifies and investigates an EC mechanism, an interfacial electron transfer (E step) followed by a solution reaction (C step), for cobalt tetraphenylporphyrin exposed to a library of organohalide electrophiles. The generally applicable workflow accurately discerns the EC mechanism's presence amid negative controls and outliers, adaptively designs desired experimental conditions, and quantitatively extracts kinetic information of the C step spanning over 7 orders of magnitude, from which mechanistic insights into oxidative addition pathways are gained. This work opens opportunities for autonomous mechanistic discoveries in self-driving electrochemistry laboratories without manual intervention.
RESUMEN
For decades, employing cyclic voltammetry for mechanistic investigation has demanded manual inspection of voltammograms. Here, we report a deep-learning-based algorithm that automatically analyzes cyclic voltammograms and designates a probable electrochemical mechanism among five of the most common ones in homogeneous molecular electrochemistry. The reported algorithm will aid researchers' mechanistic analyses, utilize otherwise elusive features in voltammograms, and experimentally observe the gradual mechanism transitions encountered in electrochemistry. An automated voltammogram analysis will aid the analysis of complex electrochemical systems and promise autonomous high-throughput research in electrochemistry with minimal human interference.
RESUMEN
A fundamental understanding of extracellular microenvironments of O2 and reactive oxygen species (ROS) such as H2O2, ubiquitous in microbiology, demands high-throughput methods of mimicking, controlling, and perturbing gradients of O2 and H2O2 at microscopic scale with high spatiotemporal precision. However, there is a paucity of high-throughput strategies of microenvironment design, and it remains challenging to achieve O2 and H2O2 heterogeneities with microbiologically desirable spatiotemporal resolutions. Here, we report the inverse design, based on machine learning (ML), of electrochemically generated microscopic O2 and H2O2 profiles relevant for microbiology. Microwire arrays with suitably designed electrochemical catalysts enable the independent control of O2 and H2O2 profiles with spatial resolution of â¼101 µm and temporal resolution of â¼10° s. Neural networks aided by data augmentation inversely design the experimental conditions needed for targeted O2 and H2O2 microenvironments while being two orders of magnitude faster than experimental explorations. Interfacing ML-based inverse design with electrochemically controlled concentration heterogeneity creates a viable fast-response platform toward better understanding the extracellular space with desirable spatiotemporal control.
Asunto(s)
Microambiente Celular , Electroquímica , Peróxido de Hidrógeno , Aprendizaje Automático , Oxígeno , Peróxido de Hidrógeno/análisis , Peróxido de Hidrógeno/metabolismo , Oxígeno/análisis , Oxígeno/metabolismo , Especies Reactivas de Oxígeno/metabolismoRESUMEN
Neural networks, trained on data generated by a microkinetic model and finite-element simulations, expand explorable parameter space by significantly accelerating the predictions of electrocatalytic performance. In addition to modeling electrode reactivity, we use micro/nanowire arrays as a well-defined, easily tuned, and experimentally relevant exemplary morphology for electrochemical nitrogen fixation. This model system provides the data necessary for training neural networks which are subsequently exploited for electrocatalytic material morphology optimizations and explorations into the influence of geometry on nitrogen fixation electrodes, feats untenable without large-scale simulations, on both a global and a local basis.
Asunto(s)
Aprendizaje Automático , Redes Neurales de la Computación , Nitrógeno/química , Técnicas Electroquímicas/instrumentación , Técnicas Electroquímicas/métodos , Electrodos , Nanocables/química , Oxidación-Reducción , Prueba de Estudio ConceptualRESUMEN
Nanoparticles have been conjugated to biological systems for numerous applications such as self-assembly, sensing, imaging, and therapy. Development of more reliable and robust biosensors that exhibit high response rate, increased detection limit, and enhanced useful lifetime is in high demand. We have developed a sensing platform by the conjugation of ß-galactosidase, a crucial enzyme, with lab-synthesized gel-like carbon dots (CDs) which have high luminescence, photostability, and easy surface functionalization. We found that the conjugated enzyme exhibited higher stability towards temperature and pH changes in comparison to the native enzyme. This enriched property of the enzyme was distinctly used to develop a stable, reliable, robust biosensor. The detection limit of the biosensor was found to be 2.9 × 10-4 M, whereas its sensitivity was 0.81 µA·mmol-1·cm-2. Further, we used the Langmuir monolayer technique to understand the surface properties of the conjugated enzyme. It was found that the conjugate was highly stable at the air/subphase interface which additionally reinforces the suitability of the use of the conjugated enzyme for the biosensing applications.