Search

Kosakonia radicincitans is a species within the new genus Kosakonia, which is typically a plant pathogen, with rare reports of human infection. The number of human infections may be underestimated because this new genus is under-represented among diagnostic tools. This report describes a case of bloodstream infection caused by K. radicincitans. The pathogen was identified by matrix-assisted laser desorption/ionization-TOF mass spectrometry and 16S rRNA gene sequencing. The hypervirulent human pathogenicity gene LON, which has not been described before, was detected in the bacterial genome by gene annotation. Thus, this discovery provides a new reference for studying the pathogenic mechanism of this rare pathogen.

Conductive nanopipettes offer promising confined spaces to enable advanced electrochemical sensing applications in small spaces. Herein, a series of metal-decorated carbon nanopipettes (CNPs) were developed, in which Au, Ag, and Pt are modified at the inner walls of CNPs by a simple electrodeposition method. The fabricated tips show good sensing performances for a variety of important analytes, such as glucose, hydrogen peroxide, and chloride and hydrogen ions in biological and catalytic systems. This simple and effective approach can be further extended to prepare other functionalized nanopipette electrodes toward more versatile and powerful measurements in electrochemical sensing and imaging applications.

Measuring the activity of low-abundance enzymes, down to a few molecules in one living cell, is important but challenging to elucidate their biological function. Here, an electrochemical molecule trap is established at the tip of a nanopipette with an electrochemical detector, in which the diffusion of the molecules away from the electrochemical detector is prevented by electro-osmotic flow (EOF). Accordingly, a limited amount of enzymes is trapped to continuously catalyze the conversion of the substrate to generate a sufficient amount of the byproduct hydrogen peroxide for electrochemical measurements. The resistive pulse sensing of the enzymes in single liposomes validates the detection sensitivity down to 15 molecules. Using this ultrasensitive electrochemical strategy, the activity of 60 sphingomyelinase molecules inside single unstimulated living J774 cells is measured, which was hardly detected by previous methods. The established electrochemical molecule trap-based sensing approach opens the door toward single-molecule electrochemical detection in one living cell. This success will solve the long-standing problem regarding the study of the activity of low-abundance proteins in cells in their native physiological state and greatly enhance the understanding of the roles of proteins in cellular behavior.

Conductive nanopipettes with both an electroactive interface and a pipet geometry have been recognized as powerful multifunctional probes in various electrochemical sensing and imaging applications. As confined inside the nanopipette, the excess surface charges at the solid/solution interface would then play a dominant role in the resulting charge transport processes. Herein, the effects of a multivalent ion on the resulting electron transfer (ET) processes in the carbon nanopipettes are investigated with both experimental and simulation methods. The multivalent cations (i.e., Ca

The electrical double layer (EDL) at solid-liquid interfaces is key to interfacial transport and reaction processes and numerous emerging applications exploiting such processes. Herein, by studying hysteresis ion-transport processes in nanopipettes near charged substrates, we found the resulting cross-point potential (Vcp) to represent the surface potential of both nanopipettes and substrates. After the subtraction of Vcp in bulk solution, the remaining ΔVcp shows excellent exponential decay with respect to the separation distance from the substrates and agrees very well with the classical double-layer theory. The revealed new hysteresis ion transport in nanopipettes would provide a new way for the simple and direct EDL imaging of various interfaces of interest with nanoscale resolution in scanning ion conductance microscopy.

The analysis of biomolecules in a 3D cell model is crucial for the collection of spatial information close to the actual organ. In this work, a highly sensitive platinized open carbon nanocavity electrode is fabricated to investigate reactive oxygen species (ROS) in three regions (proliferating zone, quiescent zone, and necrotic core) of a 3D CT26 cell model. The presence of a nanocavity permits more frequent collisions of ROS on the Pt surface, accelerating electron transfer, and thus pushes the detection limit down to 1 nM. This improved detection sensitivity guarantees the spatial investigation of the ROS distribution in a 3D cell sphere, including a high concentration in the outer proliferating layer even without any external stimulus, a low concentration in the quiescent layer, and almost no ROS at the center. The observation of ROS in the cell sphere without the stimulus reveals the presence of oxygen stress in the 3D cancer cell model, which is obviously different from the previous observation in living cultured 2D cells. This discovery provides direct evidence about the discrepancy about the metabolism in 2D and 3D cells, which could also direct a new study in cell electroanalysis to achieve more actual molecular information in life study.

Herein, we report a sensitive scanning electrochemical microscopy (SECM) method based on the high transient current signals in carbon nanopipets (CNPs) under step potential waveforms. Taking advantage of the transient peak current, the approach curve can be conducted with very dilute (1 μM) or even no redox mediator and fitted by the scanning ion conductance microscopy (SICM) theory. In addition, a trace amount of electroactive species generated at the substrate can also be directly revealed from the transient current at the CNP tips. With the established feedback and generation/collection methods, we present the constant-height topography and electroactivity imaging of the substrates with only 1 μM K

Revealing the electrocatalytic features of single redox enzyme is significant to both fundamental biological processes and practical catalysis and sensing applications. Herein, we directly reveal the electrocatalytic current from a single enzyme inside the carbon nanopipettes via electrochemical collision strategies, based on the increased activity at nanoscale confinement. Besides the staircase current steps from surface blockage, discrete H

Exploring the electrochemical collision features at nanoelectrodes is highly desirable for revealing new physical insights and further expanding its applications at smaller spaces. Herein, we study the collision processes of single silver nanoparticles (AgNPs) inside carbon nanopipettes (CNPs). Results show that AgNPs undergo multiple collision and oxidation processes prior to fully oxidation after entering into the CNPs. Different from the disk electrodes, the produced Ag+ cannot immediately diffuse away from the cavity and will be reduced once switching to reductive potentials. More intriguingly, we observe discrete cathodic spikes from the Ag+ reduction, which are presumably due to the negatively charged carbon surface confined in the CNPs. The elucidated collision features in a CNP would enable its better usage for single entity measurements at confined spaces.

Conductive nanopipettes have been widely used as a multifunctional platform for emerging sensing applications in small spaces, although the electrochemical processes involved are not well controlled and fully quantified. Herein, we use an external pressure to precisely control the solution volume and regulate the electrochemical signals in carbon nanopipettes. In addition to polarizing the redox concentration profile, the pressure is found to generate a convective flow to control the transport processes of redox molecules and nanoparticles as well, and their quantitative correlation is established by a numerical simulation. The elucidated pressure-regulated electrochemistry in conductive nanopipettes would reveal the fundamental charge transport processes at the nanoscale and promote better usage of conductive nanopipettes for delivery and sensing applications in single-cell analysis.

Unveiling the contributions of electroosmotic flow (EOF) in the electrokinetic transport through structurally-defined nanoscale pores and channels is challenging but fundamentally significant because of the broad relevance of charge transport in energy conversion, desalination and analyte mixing, micro and nano-fluidics, single entity analysis, capillary electrophoresis etc. This report establishes a universal method to diagnose and deconvolute EOF in the nanoscale transport processes through current–potential measurements and analysis without simulation. By solving Poisson, Nernst–Planck (PNP) with and without Navier–Stokes (NS) equations, the impacts of EOF on the time-dependent ion transport through asymmetric nanopores are unequivocally revealed. A sigmoidal shape in the I–V curves indicate the EOF impacts which further deviate from the well-known non-linear rectified transport features. Two conductance signatures, an absolute change in conductance and a ‘normalized’ one relative to ion migration, are proposed as EOF impact (factor). The EOF impacts can be directly elucidated from current–potential experimental results from the two analytical parameters without simulation. The EOF impact is found more significant in intermediate ionic strength, and potential and pore size dependent. The less-intuitive ionic strength and size dependence is explained by the combined effects of electrostatic screening and non-homogeneous charge distribution/transport at nanoscale interface. The time-dependent conductivity and optical imaging experiments using single nanopipettes validate the proposed method which is applicable to other channel type nanodevices and membranes. The generalizable approach eliminates the need of simulation/fitting of specific experiments and offers previously inaccessible insights into the nanoscale EOF impacts under various experimental conditions for the improvement of separation, energy conversions, high spatial and temporal control in single entity sensing/manipulation, and other related applications.

Eggerthella lenta is a normal human microflora that is anaerobic, non-sporulating, and Gram positive. However, an increasing number of studies have shown that it could also be an important pathogen for humans, even causing life-threatening infection under certain conditions. However, understanding its pathogenic mechanism and treatment options still need to be improved; more clinical data are needed to explore it further. In this article, we report a case of ceftizoxime-cured E. lenta bacteremia and review the recent literature to provide more clinical data for the diagnosis of E. lenta bacteremia. Our report suggests that the frequency of E. lenta bacteremia is increased in patients with hematologic or solid organ cancer, diabetes mellitus and also in those with appendicitis.

Conductive nanopipettes have been extensively used as powerful multifunctional probes for electrochemical and ion transport measurements, while the involved charge transfer processes have not been fully explored. In this paper, we use both experimental and simulation methods to de-convolute and quantify the respective electron transfer (ET) and ion transport (IT) contributions to the resulting current signals in carbon nanopipettes (CNPs). The results present that the current signals in CNPs are determined by ET in the case of low solution depth and long timescales, while IT becomes dominant at short timescales or high solution depth. In addition, the electrochemically and chemically irreversible ET processes in CNPs were also quantified. The elucidated and quantified charge transport processes inside CNPs will help control and optimize the IT and ET processes at the nanoscale, promoting better and broad usage of conductive nanopipettes in single-entity sensing and imaging applications., The coupled electron transfer (ET) and ion transport (IT) processes in conductive nanopipettes, at both steady and transient states, are elucidated and quantified by experiments and simulation.

In a typical intracellular electroanalytical measurement, a nanoelectrode is located inside a living cell and a reference electrode outside the cell. This setup faces a problem to drop a certain potential across the cellular plasma membrane that might interrupt the cellular activity. To solve this problem, a self-referenced nanopipette is assembled by incorporating a reference electrode inside the nanocapillary, with a Pt ring at the tip as the electrochemical surface. The potential applied between the Pt ring and the reference electrode is restricted inside the capillary and thus has a negligible effect on the surrounding cellular environment. Using this new setup, the nanopipette pierces into the nucleus of a single living cell for the measurement of hydrogen peroxide under oxidative stress. It is found that a lesser amount of hydrogen peroxide is measured in the nucleus compared with the cytoplasm, revealing uneven oxidative stress inside the cell. The result will not only greatly improve the current setup for intracellular electrochemical analysis but also provide biological information of the compartment inside the living cell.

Carbon fiber micro- and nanoelectrodes have been extensively used to measure dopamine and other neurotransmitters in biological systems. Although the radii of some reported probes were ≪1 μm, the lengths of the exposed carbon were typically on the micrometer scale, thus limiting the spatial resolution of electroanalytical measurements. Recent attempts to determine neurotransmitters in single cells and vesicles have provided additional impetus for decreasing the probe dimensions. Here, we report two types of dopamine sensors based on carbon nanopipets (CNP) prepared by chemical vapor deposition of carbon into prepulled quartz capillaries. These include 10-200 nm radius CNPs with a cavity near the orifice and CNPs with an open path in the middle, in which the volume of sampled solution can be controlled by the applied pressure. Because of the relatively large surface area of carbon exposed to solution inside the pipet, both types of sensors yielded well-shaped voltammograms of dopamine down to ca. 1 nM concentrations, and the unprecedented voltammetric response to 100 pM dopamine was obtained with open CNPs. TEM tomography and numerical simulations were used to model CNP responses. The effect of dopamine adsorption on the CNP detection limit is discussed along with the possibilities of measuring other physiologically important analytes (e.g., serotonin) and eliminating anionic and electrochemically irreversible interferences (e.g., ascorbic acid).

Nucleation and subsequent phase transitions exist broadly in nature and engineered processes, from ice formation to protein crystallization and beyond. The lack of capable methods to analyze and to control the dynamic heterogeneous process is a fundamental problem, and constitutes overwhelming technical challenges in synthesizing crystalline structures with designed/predictable properties. By actively controlling mass transport through a single nanopipette, the extent of supersaturation is adjusted kinetically in a confined space immediately outside the nanopore. Using protein insulin as prototype, the formation of a single atto-femto-liter droplet, subsequent nucleation inside and further growth of a single crystal, is monitored electrically and optically, and actively controlled by an external electrical field. The generalizable method, referred to as nanoAC for nanoscale active control, not just provides fundamental insights at unprecedented single entity resolution, it enables active in situ control o...

Microelectrodes are typically used for neurotransmitter detection, but nanoelectrodes are not because there is a trade-off between spatial resolution and sensitivity that is dependent on surface area. Cavity carbon-nanopipette electrodes (CNPEs), with tip diameters of a few hundred nanometers, have been developed for nanoscale electrochemistry. Here, we characterize the electrochemical performance of CNPEs with fast-scan cyclic voltammetry (FSCV) for the first time. Dopamine detection using cavity CNPEs, with a depth equivalent to a few radii, is compared with that using open-tube CNPEs, an essentially infinite geometry. Open-tube CNPEs have very slow temporal responses that change over time as the liquid rises in the CNPE. However, a cavity CNPE has a fast temporal response to a bolus of dopamine that is not different from that of a traditional carbon-fiber microelectrode. Cavity CNPEs, with tip diameters of 200-400 nm, have high currents because the small cavity traps and increases the local dopamine concentration. The trapping also leads to an FSCV frequency-independent response and the appearance of cyclization peaks that are normally observed only with large concentrations of dopamine. CNPEs have high dopamine selectivity over ascorbic acid (AA) because of the repulsion of AA by the negative electric field at the holding potential and the irreversible redox reaction. In mouse-brain slices, cavity CNPEs detected exogenously applied dopamine, showing they do not clog in tissue. Thus, cavity CNPEs are promising neurochemical sensors that provide spatial resolution on the scale of hundreds of nanometers, which is useful for small model organisms or for locations near specific cells.

Electrochemical experiments at individual nanoparticles (NPs) can provide new insights into their structure-activity relationships. By using small nanoelectrodes as tips in a scanning electrochemical microscope (SECM), we recently imaged individual surface-bound 10-50 nm metal NPs. Herein, we introduce a new mode of SECM operation based on tunneling between the tip and a nanoparticle immobilized on the insulating surface. The obtained current vs. distance curves show the transition from the conventional feedback response to electron tunneling between the tip and the NP at separation distances of less than about 3 nm. In addition to high-resolution imaging of the NP topography, the tunneling mode enables measurement of the heterogeneous kinetics at a single NP without making an ohmic contact with it. The developed method should be useful for studying the effects of nanoparticle size and geometry on electrocatalytic activity in real-world applications.

Better understanding in the dynamics of ion transport through nanopores or nanochannels is important for sensing, nucleic acid sequencing and energy technology. In this paper, the intriguing nonzero cross point, resolved from the pinched hysteresis current-potential (i-V) curves in conical nanopore electrokinetic measurements, is quantitatively correlated to the surface and geometric properties by simulation studies. The analytical descriptions of the conductance and potential at the cross point are developed: the cross-point conductance includes both the surface and volumetric conductance; the cross-point potential represent the overall/averaged surface potential difference across the nanopore. The impacts by individual parameter such as pore radius, half cone angle, and surface charges are systematically studied in the simulation that would be convoluted and challenging in experiments. The elucidated correlation is supported by and offer predictive guidance for experimental studies. The results also offer more quantitative and systematic insights in the physical origins of the concentration polarization dynamics in addition to ionic current rectification inside conical nanopores and other asymmetric nanostructures. Overall, the cross point serves as a simple yet informative analytical parameter to analyze the electrokinetic transport through broadly defined nanopore-type devices.

Ion transport controlled by electrostatic interactions is an important phenomenon in biological and artificial membranes, channels, and nanopores. Here, we employ carbon-coated nanopipets (CNPs) for studying permselective electrochemistry in a conductive nanopore. A significant accumulation (up to 2000-fold) of cationic redox species and anion depletion inside a CNP by diffuse-layer and surface-charge effects in a solution of low ionic strength were observed as well as the shift of the voltammetric midpeak potential. Finite-element simulations of electrostatic effects on CNP voltammograms show permselective ion transport in a single conducting nanopore and semiquantitatively explain our experimental data. The reported results are potentially useful for improving sensitivity and selectivity of CNP sensors for ionic analytes.

This paper reports on an innovative strategy based on the electrochemical collision technique to quantify the redox activity of two bacterial species: the Gram-negative Escherichia coli and the Gram-positive Bacillus subtilis. Thionine (TH), as a redox mediator, was electrostatically adsorbed on bacterial surface and formed the bacterium-TH complexes. TH can receive electrons from bacterial metabolic pathways and be reduced. When a single bacterium-TH complex collides on the ultramicroelectrode, the reduced TH will be re-oxidized at certain potential and generate current spike. The frequency of the spikes is linearly proportional to the living bacteria concentration, and the redox activity of individual bacterium can be quantified by the charges enclosed in the current spike. The redox ability of Gram-negative E.coli to the TH mediator was 6.79 ± 0.26 × 10−18 mol per bacterial cell in 30 min, which is relatively more reactive than B. subtilis (3.52 ± 0.31 × 10−18 mol per cell). The spike signals, fitted by 3D COMSOL Multiphysics simulation, revealed that there is inherent redox ability difference of two bacterial strains besides the difference in bacterial size and collision position. This work successfully quantified the bacterial redox activity to mediator in single cells level, which is of great significance to improve understanding of heterogeneous electron transfer process and build foundations to the microorganism selection in the design of microbial electrochemical devices.

Contamination with the fungus Alternaria spp. is often considered to have originated from laboratory sources, which occasionally causes infection in immunocompromised patients, termed as phaeohyphomycosis. Here, we have reported a case of cutaneous alternariosis caused by Alternaria alternata. This diagnosis was based on microscopic examination and mycological culturing of patient's vesicular lesions, with the use of 5 molecular markers (namely, ITS, ATPase, Actin, rpb2, and tef1) for strain identification. We noted that Alternaria infection caused an increase in the serum level of (1-3)-β-D-glucan (BG) in the patients. To the best of our knowledge, no such finding has been reported in previously in the literature.

Electron transfer (ET) in monolayer-protected gold clusters (Au MPCs) is crucial for revealing their fundamental energetic and kinetic properties and potential electrochemical and optical applications. In this Communication, we measured the kinetics of quantized charging processes of the Au144 MPCs. A detailed mathematical model was developed, including ET kinetics and diffusion in MPCs. The charging processes of controlled core states were treated as multistep ET reactions, and the corresponding rate constants were determined by steady-state voltammetry and scanning electrochemical microscopy (SECM).

Structurally defined nanopores have received great attention in the past decades in part due to the novel mass transport phenomena resolved at such nanoscale solid-liquid interfaces. New capabilities and/or better efficiency are envisioned in molecular sensing, energy storage and conversion, nanofluidics, and membrane transport. This review will focus on the fundamental mass transport processes confined by asymmetric nanoscale structures particularly in conical nanopores. The fabrication of different nanopore devices and the double layer theory are briefly introduced first as background. The nonlinear and dynamic mass transport processes, including ionic current rectification, dynamic concentration polarization, memory effects and capacitive charging/discharging processes are then reviewed. The fundamental understanding and quantification of dynamic transport features offer new physical insights in the nanoscale mass transport processes and has significant implications in related electroanalytical and other applications.

This paper is concerned with long-distance interactions between an unbiased metal nanoparticle (NP) and a nanoelectrode employed as a tip in the scanning electrochemical microscope (SECM). A NP immobilized on the inert substrate acts as a bipolar electrode, producing positive SECM feedback. The tip current magnitude depends strongly on the ratio of the particle and tip radii and the heterogeneous charge-transfer kinetics. The onset of electron tunneling was observed at very short separation distances (

Electron transfer activities of metal clusters are fundamentally significant and have promising potential in catalysis, charge or energy storage, sensing, biomedicine and other applications. Strong resonance coupling between the metal core energy states and the ligand molecular orbitals has not been established experimentally, albeit exciting progress has been achieved in the composition and structure determination of these types of nanomaterials recently. In this report, the coupling between core and ligand energy states is demonstrated by the rich electron transfer activities of Au130 clusters. Quantized electron transfers to the core and multi-electron transfers involving the durene-dithiolate ligands were observed at lower and higher potentials, respectively, in voltammetric studies. After a facile multi-electron oxidation from +1.34 to +1.40 V, several reversal reduction processes at more negative potentials, i.e. +0.91 V, +0.18 V and -0.34 V, were observed in an electrochemically irreversible fashion or with sluggish kinetics. The number of electrons and the shifts of the respective reduction potentials in the reversal process were attributed to the electronic coupling or energy relaxation processes. The electron transfer activities and subsequent relaxation processes are drastically reduced at lower temperatures. The time- and temperature-dependent relaxation, involving multiple energy states in the reversal reduction processes upon the oxidation of ligands, reveals the coupling between core and ligand energy states.

We report striking time-dependent ion transport characteristics at nanoscale interfaces in current–potential (I–V) measurements and theoretical analyses., The dynamics of ion transport at nanostructured substrate–solution interfaces play vital roles in high-density energy conversion, stochastic chemical sensing and biosensing, membrane separation, nanofluidics and fundamental nanoelectrochemistry. Further advancements in these applications require a fundamental understanding of ion transport at nanoscale interfaces. The understanding of the dynamic or transient transport, and the key physical process involved, is limited, which contrasts sharply with widely studied steady-state ion transport features at atomic and nanometer scale interfaces. Here we report striking time-dependent ion transport characteristics at nanoscale interfaces in current–potential (I–V) measurements and theoretical analyses. First, a unique non-zero I–V cross-point and pinched I–V curves are established as signatures to characterize the dynamics of ion transport through individual conical nanopipettes. Second, ion transport against a concentration gradient is regulated by applied and surface electrical fields. The concept of ion pumping or separation is demonstrated via the selective ion transport against concentration gradients through individual nanopipettes. Third, this dynamic ion transport process under a predefined salinity gradient is discussed in the context of nanoscale energy conversion in supercapacitor type charging–discharging, as well as chemical and electrical energy conversion. The analysis of the emerging current–potential features establishes the urgently needed physical foundation for energy conversion employing ordered nanostructures. The elucidated mechanism and established methodology can be generalized into broadly-defined nanoporous materials and devices for improved energy, separation and sensing applications.

Coating the inner wall of a quartz nanopipet with a thin layer of carbon yields a nanopore with tunable surface charge and chemical state for resistive-pulse and rectification sensing. Herein we report the experimental study and modeling of the electron-transfer gated ion transport processes in carbon nanopipets. The potential of the unbiased carbon layer can be tuned by adding very low (sub-nM) concentrations of redox species to the solution via bipolar electrochemistry. The potential of the carbon layer determines the electrical double-layer structure that, in turn, affects the ionic transport processes. The ion current rectification decreased when redox species with a relatively positive formal potential (e.g., Fe(CN)63/4–) were added to the solution and increased upon adding redox species with a negative formal potential (e.g., Ru(NH3)63/2+). Additionally, the ion current displays high sensitivity to redox species, suggesting the possibility of trace-level analysis.

Electrostatic interactions of mobile charges in solution with the fixed surface charges are known to strongly affect stochastic sensing and electrochemical energy conversion processes at nanodevices or devices with nanostructured interfaces. The key parameter to describe this interaction, surface charge density (SCD), is not directly accessible at nanometer scale and often extrapolated from ensemble values. In this report, the steady-state current-voltage (i-V) curves measured using single conical glass nanopores in different electrolyte solutions are fitted by solving Poisson and Nernst-Planck equations through finite element approach. Both high and low conductivity state currents of the rectified i-V curve are quantitatively fitted in simulation at less than 5% error. The overestimation of low conductivity state current using existing models is overcome by the introduction of an exponential SCD distribution inside the conical nanopore. A maximum SCD value at the pore orifice is determined from the fitting of the high conductivity state current, while the distribution length of the exponential SCD gradient is determined by fitting the low conductivity state current. Quantitative fitting of the rectified i-V responses and the efficacy of the proposed model are further validated by the comparison of electrolytes with different types of cations (K(+) and Li(+)). The gradient distribution of surface charges is proposed to be dependent on the local electric field distribution inside the conical nanopore.

Memristive and memcapacitive behaviors are observed from ion transport through single conical nanopores in SiO(2) substrate. In i-V measurements, current is found to depend on not just the applied bias potential but also previous conditions in the transport-limiting region inside the nanopore (history-dependent, or memory effect). At different scan rates, a constant cross-point potential separates normal and negative hysteresis loops at low and high conductivity states, respectively. Memory effects are attributed to the finite mobility of ions as they redistribute within the negatively charged nanopore under applied potentials. A quantative correlation between the cross-point potential and electrolyte concentration is established.

We proposed an in situ method for the synthesis of polyaniline (PANI)/MnO2 nanocomposite by using an in situ polymerization reaction. Morphology analysis showed a porous structure of PANI/MnO2 nanocomposite with MnO2 particles (range from 5 to 15 nm) uniformly dispersed in the polyaniline support. Thermogravimetric analysis and Fourier transform infrared spectrum revealed that the components of PANI and MnO2 in the nanocomposite can be controlled through changing the polymerization time. Toward the utility in supercapacitors, the electrochemical properties of the nanocomposite were studied using cyclic voltammetry and chronopotentiometry tests in 0.5 M Na2SO4 neutral solution. The results showed that the materials had a specific capacitance as large as 510 F g−1 in the potential range from 0.0 to 0.65 V (vs. SCE) at a charge–discharge current density of 1.0 A g−1, greatly improved compared to those of pure PANI and MnO2 materials.

Mesoporous nickel oxide with a porous structure exhibiting a bimodal pore size distribution (2.6 and 30.3 nm diameter pores) has been synthesized in this paper. Firstly, a mesoporous precursor of coordination complex Ni 3 (btc) 2 ·12H 2 O (btc = 1,3,5-benzenrtricarboxylic acid) is synthesized based on the metal–organic coordination mechanism by a hydrothermal method. Then mesoporous NiO with a bimodal size distribution is obtained by calcining the precursor in the air, and characterized by transmission electron microscopy and N 2 adsorption measurements. Such unique multiple porous structure indicates a promising application of the obtained NiO as electrode materials for supercapacitors. The electrochemical behavior has been investigated by cyclic voltammogram, electrochemical impedance spectra and chronopotentiometry in 3 wt.% KOH aqueous electrolyte. The results reveal that the prepared NiO has high-capacitance retention at high scan rate and exhibits excellent cycle-life stability due to its special mesoporous character with bimodal size distribution.

Rich and tunable physicochemical properties make noble metal clusters promising candidates as novel nanomolecules for a variety of applications. Spectroelectrochemistry analysis is employed to resolve previously inaccessible electronic transitions in Au130 clusters stabilized by a monolayer of di- and monothiolate ligands. Well-defined quantized double-layer charging of the Au core and oxidizable ligands make this Au130 nanocluster unique among others and enable selective electrolysis to different core and ligand charge states. Subsequent analysis of the corresponding absorption changes reveals that different absorption bands originate from different electronic transitions involving both metal core energy states and ligand molecular orbitals. Besides the four discrete absorption bands in the steady-state UV-visible-near-IR absorption spectrum, additional transitions otherwise not detectable are resolved upon selective addition/removal of electrons at cores and ligand energy states, respectively, upon electrolysis. An energy diagram is proposed that successfully explains the major features observed in electrochemistry and absorption spectroscopy. Those assignments are believed applicable and effective to explain similar transitions observed in some other Au thiolate clusters.