In Situ Electrochemical Rapid Induction of Highly Active γ-NiOOH Species for Industrial Anion Exchange Membrane Water Electrolyzer.

Limited by the strong oxidation environment and sluggish reconstruction process in oxygen evolution reaction (OER), designing rapid self-reconstruction with high activity and stability electrocatalysts is crucial to promoting anion exchange membrane (AEM) water electrolyzer. Herein, trace Fe/S-modified Ni oxyhydroxide (Fe/S-NiOOH/NF) nanowires are constructed via a simple in situ electrochemical oxidation strategy based on precipitation-dissolution equilibrium. In situ characterization techniques reveal that the successful introduction of Fe and S leads to lattice disorder and boosts favorable hydroxyl capture, accelerating the formation of highly active γ-NiOOH. The Density Functional Theory (DFT) calculations have also verified that the incorporation of Fe and S optimizes the electrons redistribution and the d-band center, decreasing the energy barrier of the rate-determining step (*O→*OOH). Benefited from the unique electronic structure and intermediate adsorption, the Fe/S-NiOOH/NF catalyst only requires the overpotential of 345 mV to reach the industrial current density of 1000 mA cm-2 for 120 h. Meanwhile, assembled AEM water electrolyzer (Fe/S-NiOOH//Pt/C-60 °C) can deliver 1000 mA cm-2 at a cell voltage of 2.24 V, operating at the average energy efficiency of 71% for 100 h. In summary, this work presents a rapid self-reconstruction strategy for high-performance AEM electrocatalysts for future hydrogen economy.

In Situ Observation of Glucose Metabolism Dynamics of Endothelial Cells in Hyperglycemia with a Stretchable Biosensor: Research Tool for Bridging Diabetes and Atherosclerosis.

Diabetes is a metabolic syndrome associated with hyperglycemia, hypertension, atherosclerosis, and endothelial dysfunction. Applying the mechanical stretch on cells to simulate blood circulation while monitoring the cell glucose metabolism in a high-glucose environment is important for better comprehension of the underlying mechanisms of atherosclerosis caused by diabetes. Herein, we developed a facile strategy integrating zeolitic imidazolate framework-8-encapsulated glucose oxidase (GOx@ZIF-8) and an gold (Au) stretchable electrode (Au SE) to construct a flexible and stretchable glucose sensor (GOx@ZIF-8/Au SE) for investigating the glucose metabolism mechanism of stretched endothelial cells in hyperglycemia. The encapsulation of GOx with ZIF-8 prevents the aggregation and detachment of GOx from the sensing interface and endows the biosensor with high stability. Additionally, the Au SE with inherent stretchability can act as an integrated platform for mechanical stimulation as well as for transient signal sensing during the mechanotransduction process. Moreover, this flexible and stretchable glucose sensor is successfully used for monitoring the glucose metabolism of mechanically stimulated cells in hyperglycemia, and it was found for the first time that the glucose utilization ability of cells under static conditions is higher than that in the stretched state. This facile and straightforward method paves a promising route for designing a stable enzyme-based stretchable biosensor for detecting the underlying mechanisms of atherosclerosis caused by diabetes.

Investigation of Dendrimer Transfer Behaviors at the Micro-Water/1,2-Dichloroethane Interface Facilitated by Dibenzo-18-Crown-6.

Trans-interfacial behaviors of multiple ionic species at the interface between two immiscible electrolyte solutions (ITIES) are of importance to biomembrane mimicking, chemical and biosensing, and interfacial molecular catalysis. Utilizing host-guest interaction to facilitate ion transfer is an effective and commonly used method to decrease the Gibbs energy of transfer of a target molecule. Herein, we investigated a facilitated ion transfer (FIT) process of poly(amidoamine)dendrimer (PAMAM, G0-G2) by dibenzo-18-crown-6 (DB18C6) at the microinterfaces between water and 1,2-dichloroethane (µ-W/DCE). Because of the host-guest interaction between a dendrimer and a ligand, negative shifts of the transfer potentials were observed using cyclic voltammetry or Osteryoung square wave voltammetry. From the FIT behavior of the dendrimer, we revealed that each DB18C6 could selectively coordinate with one amino group. We first evaluated the protonated status of the intermediate state (1:2) exactly under the conditions the dendrimer (G1) transfers across the interface using the electrochemical mass spectrometry (EC-MS)-hyphenated technique, which is much smaller than the protonated status in the water phase (1:8 to 14). Using the same methodology, we also studied the facilitated transfer behaviors of G0 and G2. Based on these results, we put forward the mechanism of the FIT process, which might involve a deprotonating process at the interface for higher-generation dendrimers.

Electrochemiluminescent Detection of Proteins Based on Fullerenols Modified Gold Nanoparticles and Triple Amplification Approaches.

In this work, fullerenols were found to be able to enhance the ECL signals of the luminol and H2O2 system and were employed for the first time as a reducing, catalyzing, and stabilizing agent in the one-step fast synthesis of fullerenols@AuNPs in only 5 min. First, the prepared fullerenols@AuNPs were applied to fabricate a label-free immunosensor for the detection of human cardiopathy biomarker (cardiac troponin I, cTnI). Second, using the fullerenols@AuNPs as biolabels to establish a sandwich-type immunosensor and catalyzing in situ copper-stained reaction to generate Cu particles capped on the fullerenols@AuNPs, and then a novel electrochemical stripping chemiluminescent (ESCL) method was developed for detection of cTnI and IgG with about 20 times more sensitive than the former one. At the process of ESCL detection, Cu2+was stripped from Cu@fullerenols@AuNPs with significant increase of the ECL signals. This can be attributed to the fact that the fullerenols@AuNPs nanoparticles and the Cu2+ have excellent conductivity and could facilitate the decomposition of H2O2 to generate various reactive oxygen species (ROSs), thereby accelerating the ECL process. Both immunosensors show high sensitivity and selectivity to cTnI and IgG detection with a wide linear range from fg/mL to ng/mL and the low limits of detection down to fg/mL for cTnI and IgG, respectively.

Mechanistic Study of Oxygen Reduction at Liquid/Liquid Interfaces by Hybrid Ultramicroelectrodes and Mass Spectrometry.

Proton-coupled electron transfer (PCET) reactions at various interfaces (liquid/membrane, solid/electrolyte, liquid/liquid) lie at the heart of many processes in biology and chemistry. Mechanistic study can provide profound understanding of PCET and rational design of new systems. However, most mechanisms of PCET reactions at a liquid/liquid interface have been proposed based on electrochemical and spectroscopic data, which lack direct evidence for possible intermediates. Moreover, a liquid/liquid interface as one type of soft interface is dynamic, making the investigation of interfacial reactions very challenging. Herein a novel electrochemistry method coupled to mass spectrometry (EC-MS) was introduced for in situ study of the oxygen reduction reaction (ORR) by ferrocene (Fc) under catalysis from cobalt tetraphenylporphine (CoTPP) at liquid/liquid interfaces. The key units are two types of gel hybrid ultramicroelectrodes (agar-gel/organic hybrid ultramicroelectrodes and water/PVC-gel hybrid ultramicroelectrodes), which were made based on dual micro- or nanopipettes. A solidified liquid/liquid interface can be formed at the tip of these pipettes, and it serves as both an electrochemical cell and a nanospray emitter for mass spectrometry. We demonstrated that the solidified L/L interfaces were very similar to typical L/L interfaces. Key CoTPP intermediates of the ORR at the liquid/liquid interfaces were identified for the first time, and the four-electron oxygen reduction pathway predominated, which provides valuable insights into the mechanism of the ORR. Theoretical simulation has further supported the possibility of formation of intermediates. This type of platform is promising for in situ tracking and identifying intermediates to study complicated reactions at liquid/liquid interfaces or other soft interfaces.

Potential-Resolved Multicolor Electrochemiluminescence for Multiplex Immunoassay in a Single Sample.

Electrochemiluminescence (ECL) is a highly successful technique used in commercial immunoassays for clinical diagnosis. Developing an ECL-based multiplex immunoassay, with the potential to enable high-throughput detection of multiple biomarkers simultaneously, remains a current research interest yet is limited by a narrow choice of ECL luminophores. Herein we report the synthesis, photophysics, electrochemistry, and ECL of several new ruthenium(II) and iridium(III) complexes, three of which are eventually used as signal reporters for multiplex immunoassay. The ECL behaviors of individual luminophores and their mixtures were investigated in multiple modes, including light intensity, spectrum, and image measurements. The spectral peak separation between Ru(bpy)2(dvbpy)2+ (bpy = 2,2'-bipyridine, dvbpy = 4,4'-bis(4-vinylphenyl)-2,2'-bipyridine), and Ir(dFCF3ppy)2(dtbbpy)+ (dFCF3ppy = 3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl]phenyl, dtbbpy = 4,4'-bis( tert-butyl)-2,2'-bipyridine) was up to 145 nm, thus providing the spectrum-resolved possibility of identifying light signals. The potential-resolved ECL signals were achieved for the mixtures of Ir(ppy)3 (ppy = 2-phenylpyridine) with either Ru(bpy)2(dvbpy)2+ or Ir(dFCF3ppy)2(dtbbpy)+, due to the self-annihilation ECL of Ir(ppy)3 at higher potentials, as confirmed by electrochemistry-coupled mass spectrometry. A multiplex immunoassay free of spatial spotting antibodies on plates or substrates was ultimately devised by combining luminophore-loaded polymer beads with the homogeneous sandwich immunoreaction. Using potential and spectrum dual-resolved ECL as the readout signal, simultaneous recognition of three antigens, namely, carcinoembryonic antigen (CEA), alpha-fetoprotein (AFP), and beta-human chorionic gonadotropin (ß-HCG), was demonstrated in a single run for a sample volume of 300 µL. These results contribute to the understanding of ECL generation by multiple luminophores and devising spot-free multiplex immunoassays with less sample consumption.

Triethanolamine-Modified Gold Nanoparticles Synthesized by a One-Pot Method and Their Application in Electrochemiluminescent Immunoassy.

In many electrochemiluminescent (ECL) systems, coreactants play crucial roles in the redox-induced light emission process at the electrode surface. In this work, a novel and environment-friendly nanoplatform for ECL immunosensing enabled by triethanolamine (TEOA)-modified gold nanoparticles (TEOA@AuNPs) is reported. The monodisperse TEOA@AuNPs are fabricated by one-pot synthesis using TEOA as both reducing and stabilizing agent. Then the TEOA@AuNPs-modified electrode not only acted as coreactant for Ru(bpy)32+ ECL system but also provided a carrier for antibody 1 to form label-free immunosensor through an interaction between antigen and antibody. The unique structure of the TEOA@AuNPs loaded a large amount of coreactant of Ru(bpy)32+, which shortened the electron-transfer distance from the AuNPs surface to the appended TEOA molecules, thereby greatly enhancing the ECL efficiency and amplifying the ECL signal. In addition, Ru(bpy)32+-doped silica (RuSiO2) nanoparticles and antibody 2 were combined to form a composite for labels and a sandwich-type ECL immunosensor has been constructed. The possible mechanism of those ECL systems have also been proposed and confirmed by the EC-MS hyphenated technique. The human cardiopathy biomarker, cardiac troponin I (cTnI), was detected in a wide linear concentration range and the limit of detection (LOD) was 34 or 5.5 fg mL-1 by using the proposed label-free or labeling ECL immunoassay method.

Three-dimensional flexible and stretchable gold foam scaffold for real-time electrochemical sensing in cells and in vivo.

Compared with typical two-dimensional electrodes, the three-dimensional (3D) cell culture platform can simulate the real cell survival environment for cell growth to accurately reproduce cell functions. Moreover, considering that living cells are exposed to various of mechanical force in the microenvironment, the construction of 3D electrodes with excellent flexible, stretchable, and biocompatibility is of great significance to real-time monitor mechanically evoked biomolecule release from cells. Herein, we demonstrated a straightforward and effective three-step approach to fabricate three-dimensional flexible and stretchable gold foam scaffold (3D Au foam scaffold) for construction of 3D cell culture integrated electrochemical sensing platform. The excellent biological and electrical properties of Au nanostructures and porous networks of the 3D scaffold endow the platform with desirable biocompatibility and sensitive electrochemical sensing performance. As a proof of concept, the 3D Au foam scaffold functionalized with cobalt based nanocubes (Co NCs/Au foam scaffold) was validated to provide 3D culture for human umbilical vein endothelial cells (HUVECs), and synchronously real-time monitor superoxide anion (O2•-) released by HUVECs under mechanical stretching. Furthermore, 3-mercaptopropionic acid (3-MPA) modified 3D Au foam (3-MPA/Au foam scaffold) was successfully used for real-time monitoring of catecholamines in rat brain. The results demonstrate the great potential of this 3D Au foam scaffold for real-time electrochemical monitoring biomolecules in vitro and in vivo, providing convenience for future research on mechanotransduction relevant processes.

Bioinspired Structure Regulation of Apyrase-Like Nanozyme with Intracellular-Generated H2O2 for Tumor Catalytic Therapy.

Adenosine triphosphate (ATP) is the major resource of energy supply in tumor activity. Therefore, improving ATP consumption efficiencies is a promising approach for cancer therapy. Herein, inspired by the H2O2-involved structure regulation effect during the catalysis of natural protein enzymes, we developed an artificial H2O2-driven ATP catalysis-promoting system, the Ce-based metal-organic framework (Ce-MOF), for catalytic cancer therapy. In the presence of H2O2, the hydrolysis ATP activity of Ce-MOF(H2O2) was enhanced by around 1.6 times. Taking advantage of the endogenous H2O2 in cancerous cells, catalytic hydrolysis for intracellular ATP of the Ce-MOF achieves the inhibition of cancerous cell growth, which involves damaged mitochondrial function and autophagy-associated cell death. Furthermore, in vivo studies suggest that the Ce-MOF has a good tumor inhibition effect. The artificial H2O2-driven ATP catalysis-promoting system not only demonstrates high catalytic ATP consumption efficiencies for cancer therapy but also highlights a bioinspired strategy to expedite nanozyme research in both design and applied sciences.

Revealing the Sulfur Redox Paths in a Li-S Battery by an In Situ Hyphenated Technique of Electrochemistry and Mass Spectrometry.

The lithium-sulfur (Li-S) battery is one of the most promising next generation energy storage systems due to its high theoretical specific energy. However, the shuttle effect of soluble lithium polysulfides formed during cell operation is a crucial reason for the low cyclability suffered by current Li-S batteries. As a result, an in-depth mechanistic understanding of the sulfur cathode redox reactions is urgently required for further advancement of Li-S batteries. Herein, the direct observation of polysulfides in a Li-S battery is reported by an in situ hyphenated technique of electrochemistry and mass spectrometry. Several short-lived lithium polysulfide intermediates during sulfur redox have been identified. Furthermore, this method is applied to a mechanistic study of an electrocatalyst that has been observed to promote the polysulfides conversion in a Li-S cell. Through the abundance distributions of various polysulfides before and after adding the electrocatalyst, compelling experimental evidences of catalytic selectivity of cobalt phthalocyanine to those long-chain polysulfide intermediates are obtained. This work can provide guidance for the design of novel cathode to overcome the shuttle effect and facilitate the sulfur redox kinetics.