Micro ring–disk electrode probes for scanning electrochemical microscopy

The construction and characterisation of ring–disk (RD) microelectrodes suitable for use in scanning electrochemical microscopy (SECM) is reported. Such RD electrodes are proposed as probes for novel generator–collector SECM experiments. In this case, the interaction of both the reactants and products with the substrate under investigation can be followed simultaneously from a single approach curve to the substrate. Examples of such approach curves to conducting and insulating substrates are given to demonstrate the potential of this new mode of SECM operation.     

Ion beam induced deposition of platinum carbon composite electrodes for combined atomic force microscopy–scanning electrochemical microscopy

In the present study, ion beam induced deposition (IBID) of platinum carbon (PtC) composite electrodes is evaluated for combined atomic force microscopy–scanning electrochemical microscopy (AFM–SECM) probes. After deposition, the PtC composite materials are post-treated using focused ion beam (FIB) milling to decrease the carbon content of the material. It is shown that this treatment leads to an improvement of electrode characteristics for selected analytes, including the oxidation of potassium hexacyanoferrate(II) trihydrate (Fe(CN)₆^4?) and hydrogen peroxide (H₂O₂). Moreover, the proposed approach is compatible with microfabricated AFM–SECM probes for increasing the AFM tip-integrated electroactive area while maintaining the geometric dimensions, which is important for imaging biosensor development.     

RNA aptamer-based optical nanostructured sensor for highly sensitive and label-free detection of antigen–antibody reactions

Developments of optical protein sensors with nanostructure based on the noble metals have currently received great attention for their high efficiency and simultaneous analysis of various important biomolecules from proteomics to genetics. In this study, we exploited the absorbance spectra of gold-capped nanoparticles substrate for label-free detections of antigen–antibody reactions using a specific thiolated RNA aptamer. These synthesized RNA aptamers have been optimized to bind to the Fc portion of the human IgG1 subclass, due to their ability to orient antibodies direction on the gold surface. After attaching the anti-fibrinogen antibodies on the surface via these linkers, our thiolated RNA aptamer-based nanostructured sensors were easily applicable to specific detections of fibrinogen with a limit of detection of 0.1 ng/mL. These nanostructured sensor-based models will open a way to display numerous immunosensors as well as to develop other functionally similar sensors which could then be expanded into multi-arrays assay systems.     

The application of scanning electrochemical microscopy to the discovery of Pd–W electrocatalysts for the oxygen reduction reaction that demonstrate high activity, stability, and methanol tolerance

An array of Pd–W alloys was fabricated, and the electrocatalytic activity of the alloys for the oxygen reduction reaction (ORR) in acidic media was screened by scanning electrochemical microscopy. The Pd_0.7W_0.3 showed the highest activity for the ORR, close to that for Pd_0.8Co_0.2 and Pt. A Pd–W electrocatalyst loaded on carbon black was formed by the NaBH₄-reduction method, exhibiting high activity and stability, suggesting that it is a good candidate for the proton exchange membrane fuel cell cathode.     

β-Sonogel-Carbon electrodes: A new alternative for the electrochemical determination of catecholamines

In this work, a new alternative for the electrochemical determination of catecholamines based on β-cyclodextrin-Sonogel-Carbon electrodes is reported. The incorporation of β-CD and graphite in the preparation of the Sonogel-Carbon material leads to a modification of the electrode surface properties which causes a significant increase in the oxidation peak current of biomolecules such as dopamine, l-epinephrine, d,l-norepinephrine and catechol. This phenomenon might be attributed to the formation of an inclusion complex between β-CD and the catecholamines. The amount of β-CD necessary to form the Sonogel electrode was studied and optimization of electrochemical parameters, perm selectivity and mechanical stability of the sensor are discussed. Scanning electron microscopy and electrochemical impedance spectroscopy measurements were employed to characterize the electrical parameters and the structural properties of the new electrode surface, respectively. Cyclic voltammetry (CV) and Adsorptive differential pulse voltammetry (AdDPV) measurements were also used to explore the electrochemical behaviour of the electrode versus the quoted catecholamines. The β-CD-Sonogel-Carbon electrode offers fast and linear responses towards dopamine, norepinephrine, epinephrine and catechol, with good and low detection limits: 0.164, 0.294, 0.699 and 0.059 μmol L⁻¹, respectively.     

Recent advances in high resolution scanning electrochemical microscopy of living cells – A review

This review discusses advances in the field of high resolution scanning electrochemical microscopy (HR-SECM) and scanning ion conductance microscopy (SICM) to study living cells. Relevant references from the advent of this technique in the late 1980s to most recent contributions in 2012 are presented with special discussion on high resolution images. A clear progress especially within the last 5 years can be seen in the field of HR-SECM. Furthermore, we also concentrate on the intrinsic properties of SECM imaging techniques e.g. different modes of image acquisition, their advantages and disadvantages in imaging living cells and strategies for further enhancement of image resolution, etc. Some of the recent advances of SECM in nanoimaging have also been discussed which may have potential applications in high resolution imaging of cellular processes.     

A functional feature analysis on diverse protein–protein interactions: application for the prediction of binding affinity

Protein–protein interactions (PPIs) play crucial roles in diverse cellular processes. There are different types of PPIs based on the composition, affinity and whether the association is permanent or transient. Analyzing the diversity of PPIs at the atomic level is crucial for uncovering the key features governing the interactions involved in PPI. A systematic physico-chemical and conformational studies were implemented on interfaces involved in different PPIs, including crystal packing, weak transient heterodimers, weak transient homodimers, strong transient heterodimers and homodimers. The comparative analysis shows that the interfaces tend to be larger, less planar, and more tightly packed with the increase of the interaction strength. Meanwhile the strong interactions undergo greater conformational changes than the weak ones involving main chains as well as side chains. Finally, using 18 features derived from our analysis, we developed a support vector regression model to predict the binding affinity with a promising result, which further demonstrate the reliability of our studies. We believe this study will provide great help in more thorough understanding the mechanism of diverse PPIs.     

A new strategy for label-free electrochemical immunoassay based on “gate-effect” of β-cyclodextrin modified electrode

A novel label-free electrochemical immunoassay was developed for prostate-specific antigen (PSA) detection via using β-cyclodextrin (β-CD) assembled layer created gates for the electron transfer of probe. To construct the sensor, a gold electrode was self-assembled with monoclonal anti-PSA antibody labeled 6-mercapto-β-cyclodextrin. Interspaces among β-CD molecules in the layer were automatically formed on gold electrode, which act as the channel of the electron transfer of [Fe(CN)₆]^3−/4− probe. When PSA bind with anti-PSA, it can block these channels on the electrode surface due to their steric hindrance effect, resulting in the decrease in redox current of the probe. Through such a gate-controlled effect, ultra trace amount of PSA may make the currents change greatly after the immunoreaction, which enhanced the signal-to-noise ratio to achieve the amplification effect. By evaluating the logarithm of PSA concentrations, the immunosensor had a good linear response to the current changes with a detection limit of 0.3 pg/mL (S/N = 3) when PSA concentration ranged from 1.0 pg/mL to 1.0 ng/mL. The label-free immunosensor exhibited satisfactory performances in sensitivity, repeatability as well as specificity.     

Ratiometric electrochemical detection of Pd•••π interactions: application towards electrochemical molecular logic gates

Abstract

The widespread and large scale use of platinum group metals, especially palladium, in a wide variety of industrial applications has seen their levels in wastewater streams, roadside dust and even pharmaceuticals significantly rise over recent years. Due to the possible environmental damage and potential health risk this may cause, there is now substantial demand for inexpensive, efficient and robust methods for the detection of palladium. Based upon self-immolative linker technologies, we have designed and synthesised a number of allyl ether-functionalised electrochemical probes to determine the optimum probe structure required to deliver a ratiometric electrochemical detection method capable of achieving a limit of detection of <1 mg/mL within 20 min through the use of disposable screen-printed carbon electrodes. Combined with an enzymatic assay, this method was then used to achieve a proof-of-principle ratiometric electrochemical molecular logic gate.     

Simultaneous pit generation and visualization of pit topography using combined atomic force–scanning electrochemical microscopy

Combined atomic force microscopy–scanning electrochemical microscopy (AFM–SECM) is for the first time used to generate single corrosion pits on passivating iron surfaces in the micrometer range. The AFM–SECM probe locally generates nitric acid during the oxidation of nitrite ions with the release of protons at selected sites on the surface of the otherwise passive metal. High confinement of passive film breakdown is achieved from the combination of a small probe size and the inhibiting properties of non-reacted nitrite ions on the surrounding passivated surface. Simultaneous visualization of pit nucleation and propagation can be obtained in the same solution without changing the probe by AFM.     

A new sequence based encoding for prediction of host–pathogen protein interactions

Pathogen–host interactions are very important to figure out the infection process at the molecular level, where pathogen proteins physically bind to human proteins to manipulate critical biological processes in the host cell. Data scarcity and data unavailability are two major problems for computational approaches in the prediction of pathogen–host interactions. Developing a computational method to predict pathogen–host interactions with high accuracy, based on protein sequences alone, is of great importance because it can eliminate these problems. In this study, we propose a novel and robust sequence based feature extraction method, named Location Based Encoding, to predict pathogen–host interactions with machine learning based algorithms. In this context, we use Bacillus Anthracis and Yersinia Pestis data sets as the pathogen organisms and human proteins as the host model to compare our method with sequence based protein encoding methods, which are widely used in the literature, namely amino acid composition, amino acid pair, and conjoint triad. We use these encoding methods with decision trees (Random Forest, j48), statistical (Bayesian Networks, Naive Bayes), and instance based (kNN) classifiers to predict pathogen–host interactions. We conduct different experiments to evaluate the effectiveness of our method. We obtain the best results among all the experiments with RF classifier in terms of F1, accuracy, MCC, and AUC.     

Synthesis of Au–ZnS hybrid nanostructures and their application for electrochemical biosensor

Au–ZnS core–shell nanostructures were grown onto the transparent indium tin oxide (ITO) thin film-coated glass surface by successive electrodeposition of Au and ZnS in cyclic voltammetry. The resulting hybrid nanostructures were characterized using scanning electron microscopy, X-ray diffraction, UV–vis spectroscopy, and electrochemical impedance spectroscopy. The glucose oxidase (GOD) was immobilized onto the surface of the Au–ZnS hybrid nanostructures in silica sol–gel network. Furthermore, the Au–ZnS nanostructures demonstrate an enhanced direct electron transfer between GOD and the electrode due to their unique chemical and electrocatalytic properties and their synergy effect. The analytical performance of the GOD-based electrode was improved greatly compared with that of ITO substrate modified by Au or ZnS nanostructures alone. The proposed enzyme electrode based on Au–ZnS hybrid nanomaterials displays high sensitivity and wide linear range in the determination of glucose. The Au–ZnS hybrid nanostructures have potential for “green chemistry” application in the fabrication of enzyme-based electrochemical biosensors.     

A new method for the synthesis of organic–polyoxometallate hybrid compounds

The reaction of the Na₂MoO₄ or Na₂WO₄ salt with organic amine and PCl₅, SiCl₄ or TiCl₄ in hydrochloric acid medium under hydrothermal conditions yields organic–polyoxometallate hybrid compounds, with the following reaction formula: Na₂MO₄ + Lewis-base + XCl_n + HCl → (Lewis-baseH)_m(XM₁₂O₄₀) + NaCl + H₂O (M = Mo or W; X = P, Si, Ti,; n = 3–5). By using this method, four new complexes, [(CH₃)₂NH]₃[H₃PW₁₂O₄₀] (1), (C₂H₅OH)₃(H₃PMo₁₂O₄₀) (2), [DMDA]₂[H₄SiW₁₂O₄₀]·H₂O (3) (DMDA = 1 N,3 N-dimethyl-1,3-diazolidine) and [(DAN)₆][H₄TiW₁₂O₄₀]·4H₂O (DAN = 4,4′-dianiline) (4), were obtained, and their crystal structures are reported. Thermal analysis of 1, 2 and 4 has been carried out. The thermal analysis indicates that the Keggin anion skeleton begins to decompose at about 300 °C. The possibility of constructing hydrogen-bond interactions by association between the polyoxometallate and the organic compound is explored. The roles of solvents and organic groups in the formation of specific crystalline architectures are discussed. The crystal structure of [H₄TiW₁₂O₄₀], a hetero-transition-metal Keggin polyoxometallate with a square-plane TiO₄, has been reported. Four architectures developed by hydrogen-bond associations of different Keggin polyoxometallates and organic bearing N–H or O–H donor functions are described. The selected organic modules (4,4′-dianiline, 1,3-dimethylimidazolidine, dimethylamine and ethanol) possess hydrogen-donor functions to allow them to act as bridges between polyoxometallate groups. Depending on the nature of the donor group, the number of hydrogens available for bonding, the geometric features and the sizes of the organic modules, diverse assembling patterns have been observed ranging from one-dimensional to three-dimensional networks. For all the networks, H₃O⁺ and H⁺ act as actual linkers between the molecular units.     

Phosphorus–nitrogen compounds: Part 19. Syntheses,structural and electrochemical investigations,biological activities,and DNA interactions of new spirocyclic monoferrocenylcyclotriphosphazenes

The reactions of hexachlorocyclotriphosphazatriene, N₃P₃Cl₆, with N-alkyl-N-ferrocenylmethylethylene diamines, FcCH₂NH(CH₂)₂NHR₁ [R₁ = Me (1) and Et (2)], and sodium [3-(N-ferrocenylmethylamino)-1-propanoxide] (3) produce spirocyclic monoferrocenyl tetrachlorophosphazenes (1a–3a). The tetrapyrrolidinophosphazenes (1b–3b) are prepared from the reactions of corresponding phosphazenes (1a–3a) with excess pyrrolidine. The reaction of 1a with excess morpholine affords geminal-morpholino phosphazene (1c), whilst the reactions of 2a and 3a give diethylaminotrimorpholino (2c) and fully substituted morpholino products (3c), respectively. The structural investigations of the compounds are examined by Fourier transform IR, MS, ¹H, ¹³C, ³¹P NMR, DEPT, HETCOR, and HMBC techniques. The crystal structures of 3b and 3c are determined using X-ray crystallography. Cyclic voltammetric and chronoamperometric data show that compounds 1a–3a, 1b–3b, and 1c–3c exhibit electrochemically reversible one-electron oxidation of Fc redox centers which are hardly affected by the substituents on the phosphazene ring. The compounds 1b, 2b, 3b, and 3c are screened for antibacterial activities against Gram-positive and Gram-negative bacteria and for antifungal activities against yeast strains. In addition, the antituberculosis activities (in vitro) of these compounds are evaluated against INH-susceptible reference strain M. tuberculosis H37Rv, and six multi-drug resistant clinical M. tuberculosis isolates. Compound 2b is found to be the most active against the susceptible the reference strain. In addition, 1b, 2b, and 3c are active against all the multidrug-resistant clinical isolates at the highest concentrations. Gel electrophoresis data indicate that the compounds promote the formation of strand breaks in plasmid DNA. Almost all the concentrations lost of supercoiled DNA suggests that the compound 3b is very efficient plasmid-modifier. The compounds inhibit BamHI cleavage of pUC18 DNA while restricting HindIII.     

A new transformation for the Lotka–Volterra problem

The Lotka–Volterra dynamical system is reduced to a single secondorder autonomous ordinary differential equation by means of a new variable transformation. Formal analytic solutions are presented for this latter differential equation.     

Electrospinning of GeO_2–C fibers and electrochemical application in lithium-ion batteries

GeO_2–C fibers were successfully synthesized using electrospinning homogeneous sol and subsequent calcination in an inert atmosphere. The spinnable sol was prepared by adding polyacrylonitrile(PAN)and polyvinylpyrrolidone(PVP) in a weight ratio of 1:1 into a mixture with white precipitate produced by dropping GeCl_4 into DMF. X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS),thermogravimetric analysis(TGA), scanning electron microscopy(SEM) and transmission electron microscopy(TEM) were employed to characterize the as-obtained fibers, and electrochemical tests were conducted to measure electrochemical performance of the electrode. The electrospun fibers have uniform diameters of 300 nm. After being calcined at 600 8C for 2 h in Ar, they transform to amorphous GeO_2–C fibers with the same morphologies. The Ge O_2–C fibers exhibit excellent cycling stability with a high reversible capacity of 838.93 m A h g~(-1)after 100 cycles at a current density of 50 m A g~(-1), indicating the composite fibers could be promising anode candidates for lithium-ion batteries.     

Microchannel chips for the multiplexed analysis of human immunoglobulin G–antibody interactions by surface plasmon resonance imaging

We report the multiplexed, simultaneous analysis of antigen–antibody interactions that involve human immunoglobulin G (IgG) on a gold substrate by the surface plasmon resonance imaging method. A multichannel, microfluidic chip was fabricated from poly(dimethylsiloxane) (PDMS) to selectively functionalize the surface and deliver the analyte solutions. The sensing interface was constructed using avidin as a linker layer between the surface-bound biotinylated bovine serum albumin and biotinylated anti-human IgG antibodies. Four mouse anti-human IgG antibodies were selected for evaluation and the screening was achieved by simultaneously monitoring protein–protein interactions under identical conditions. Antibody–antigen binding affinities towards human immunoglobulin were quantitatively compared by employing Langmuir adsorption isotherms for the analysis of SPRi responses obtained under equilibrium conditions. We were able to identify two IgG samples with higher affinities towards the target, and the determined binding kinetics falls within the typical range of values reported in the literature. Direct measurement of proteins in serum samples by SPR imaging was achieved by developing methods to minimize nonspecific adsorption onto the avidin-functionalized surface, and a limit of detection (LOD) of 6.7 nM IgG was obtained for the treated serum samples. The combination of SPR imaging and multichannel PDMS chips offers convenience and flexibility for sensitive and label-free measurement of protein–protein interactions in complex conditions and enables high-throughput screening of pharmaceutically significant molecules. Figure Microchannel SPR imaging for protein–protein interactions     

Characterization and application of quantum dot nanocrystal–monoclonal antibody conjugates for the determination of sulfamethazine in milk by fluoroimmunoassay

Quantum dot (Qdot) nanocrystals have been increasingly used as fluorescence labels in fluoroimmunoassays recently because of their excellent optical characteristics. In this paper, a new monoclonal antibody (MAb) against sulfamethazine (SMZ) was successfully produced and linked to Qdot nanocrystals by covalent coupling. The Qdot–MAb conjugates were characterized by SDS-PAGE and high-performance capillary electrophoresis (HPCE). An enzyme-linked immunosorbent assay (ELISA) method was utilized to evaluate the antigen–antibody binding affinity and then a novel direct competitive fluorescence-linked immunosorbent assay (cFLISA) for the detection of SMZ in milk by using Qdots as fluorescent labels was evaluated. The results showed that the 50% inhibition values (IC₅₀) of the cFLISA were 4.3 ng/mL in milk and 5.2 ng/mL in PBS, and the limits of detection (LODs) were 0.6 ng/mL in milk and 0.4 ng/mL in PBS, respectively. The recoveries of SMZ from spiked milk samples at levels of 10–100 ng/mL ranged from 94 to 106%, with coefficients of variation (CVs) of 2.1–9.2%. Figure Shematic diagram of the direct cFLISA procedure Jianzhong Shen and Fei Xu contributed equally to this work.     

Plasmonics for the study of metal ion–protein interactions

The study of metal–protein interactions is an expanding field of research investigated by bioinorganic chemists as it has wide applications in biological systems. Very recently, it has been reported that it is possible to study metal–protein interactions by immobilizing biomolecules on metal surfaces and applying experimental approaches based on plasmonics which have usually been used to investigate protein–protein interactions. This is possible because the electronic structure of metals generates plasmons whose properties can be exploited to obtain information from biomolecules that interact not only with other molecules but also with ions in solution. One major challenge of such approaches is to immobilize the protein to be studied on a metal surface with preserved native structure. This review reports and discusses all the works that deal with such an expanding new field of application of plasmonics with specific attention to surface plasmon resonance, highlighting the advantages and drawbacks of such approaches in comparison with other experimental techniques traditionally used to study metal–protein interactions.

Fine tuning of the structure of phosphine–phosphoramidites: application for rhodium-catalyzed asymmetric hydrogenations

Diastereomers of (4-(diphenylphosphino)pentan-2-yl)-N-isopropyl-{dinaphtho[2,1-d:1′,2′-f][1,3,2]dioxa-phosphepin-2-yl}-4-amine, (S)-(2S,4S)-1, and (S)-(2R,4R)-3; the octahydro derivative 4 of (S)-(2S,4S)-1, and derivative 2 of (S)-(2S,4S)-1 containing a 1,3-propanediyl backbone, have been synthesized and used for rhodium-catalyzed asymmetric hydrogenations of prochiral olefins in order to study the role of the stereogenic elements in the backbone and in the terminal moiety. The central chirality in the bridge has been found to determine the configuration of the product with a cooperative effect from the terminal groups. Excellent ee’s (up to 99.9%) were obtained in the hydrogenation of methyl (Z)-α-acetamidocinnamate using a rhodium complex with the matched arrangement (S)-(2S,4S)-1. The hydrogenation is accomplished in a highly enantioselective manner by using green solvents such as propylene carbonate.