Surface patterning using scanning electrochemical microscopy to locally trigger a “click” chemistry reaction

We report on the surface micropatterning of conductive surfaces via the electrochemical triggering of a click reaction, the copper(I) catalyzed azide–alkyne cycloaddition reaction (CuAAC) by SECM via a two-step approach: (i) functionalization on the entire surface with azido-aryl groups by using the diazonium approach followed by (ii) the covalent linkage of alkyne-bearing ferrocene by CuAAC within a local area by SECM. More precisely, the click reaction was triggered by Cu(I) catalyst generation for 30 min at the SECM tip positioned ≈ 10 μm above the azido-aryl modified surface. The dimension of the spot obtained under these conditions was ≈ 75 μm. The electrochemical imaging by SECM of the ultra thin area locally clicked with ferrocene moieties was made thanks to the electrocatalytic properties of the ferrocene modified surface towards ferrocyanide electrooxidation. This local clicking procedure opens the gate to further controlled functionalization of restricted small substrates.     

Alternating current (AC) impedance imaging with combined atomic force scanning electrochemical microscopy (AFM-SECM)

AFM-SECM measurements using alternating current mode SECM (AC–SECM) were performed at an AFM tip with an integrated recessed ring microelectrode. Measurements were carried out in a three-electrode arrangement at 14.92 kHz and 110 mV_pp in 1 mM KCl solution. Combined AFM–AC–SECM enables the detection of electrochemical surface properties with high lateral resolution without addition of a redox mediator, thereby providing images on topographical changes along with chemical information. For demonstrating the capabilities of this method, simultaneously recorded data on the topography and the surface conductivity of gold/glass structures and of microelectrode arrays are discussed.     

Morphology and properties of hollow-fiber membrane made by PAN mixing with small amount of PVDF

In this paper, the morphological structure and properties such as, miscibility, tensile strength, flux and retention ratio of hollow-fiber membranes manufactured by PAN mixing with small amounts of PVDF have been studied. The hollow fiber was made from a spinning solution composed of polymer (PAN : PVDF=10 : 0, 9 : 1, 7 : 3), additive (PVP, PEG-600) and solvent (DMAC) when immersed in water. The spinnability of blend polymer and the influences of blending on spinning technology have been observed; the morphology of membranes were examined by SEM. The blend membranes possess much higher flux than PAN membrane and fairly good retention ratio especially for the membrane made by PAN : PVDF=9 : 1.     

Signal enhancement in solution-cathode glow discharge — optical emission spectrometry via low molecular weight organic compounds

HCOOH, CH₃COOH, and CH₃CH₂OH were used as chemical modifiers in a solution-cathode glow discharge. Emission was measured directly from the discharge, without a gas–liquid separator or a secondary excitation source. Emission from Ag, Se, Pb, and Hg was strongly enhanced, and the detection limits (DL) for these elements were improved by up to an order of magnitude using a combination of HCOOH and HNO₃ compared to using HNO₃ alone. The DL was measured for Mg (1 μg/L), Fe (10 μg/L), Ni (6 μg/L), Cu (6 μg/L), Pb (1 μg/L), Ag (0.1 μg/L), Se (300 μg/L), and Hg (2 μg/L). Coefficients of determination (R²) were between 0.9986 and 0.9999. A voltage of 1 kV was used, which produced a current of approximately 70 mA.     

Photocurrent generated on a carotenoid-sensitized TiO2 nanocrystalline mesoporous electrode

Photocurrent was observed upon monochromatic illumination of an ITO electrode coated with a TiO₂ nanocrystalline mesoporous membrane with carotenoid 8′-apo-β-caroten-8′-oic acid (ACOA) deposited as a sensitizer (illuminated area 0.25 cm²) and immersed in an aqueous 10 mM hydroquinone (H₂Q), 0.1 M NaH₂PO₄ solution (pH = 7.4) purged with argon, using a platinum flag counter electrode (area 3.3 cm²) and a SCE reference electrode. The carotenoid-sensitized short-circuit photocurrent reached 4.6 μA/cm² upon a 40 μW/cm² incident light beam at 426 nm, with an IPCE (%, incident monochromatic photon-to-photocurrent conversion efficiency) as high as 34%. The short-circuit photocurrent was stable during 1 h of continuous illumination with only a 10% decrease. An open-circuit voltage of 0.15 V was obtained (upon 426 nm, 40 μW/cm² illumination) which remained at a constant value for hours. The observed open-circuit voltage is close to the theoretical value (0.22 V) expected in such a system. The action spectrum resembled the absorption spectrum of ACOA bound on the TiO₂ membrane with a maximum near 426 nm. No decay of the ACOA on the TiO₂ surface was observed after 12 h, presumably because of rapid regeneration of ACOA from ACOA⁺ at the surface by electron transfer from H₂Q.     

Self-healing characteristic of praseodymium conversion coating on AZNd Mg alloy studied by scanning electrochemical microscopy

Application of rare earth conversion coatings as a surface treatment for magnesium has been the subject of several studies revealing the potential to act as an effective passivating layer. Herein a mechanistic study is presented on the formation of a rare earth conversion layer based on Pr(NO₃)₃ on AZ80X magnesium alloy in simulated biological (buffered) solution. Scanning electrochemical microscopy (SECM) was used to investigate the insulating properties and degradation behaviour of the Pr conversion layer. The self-healing properties of the conversion layer in the presence of Pr^3 + were also studied using SECM. Results revealed the self-healing characteristic of the Pr conversion film in the presence of active, Pr^3 +, species. The Pr conversion layer provided passivation in the short term by producing an electrochemically inert and insulating layer. SECM results in potentiometric mode elucidated the role of near surface pH in the formation of the conversion coating.     

Development of an ionic liquid modified screen-printed graphite electrode and its sensing in determination of dopamine

A novel screen-printing ink consisted of graphite, cellulose acetate and ionic liquid n-octylpyridinum hexafluorophosphate (OPPF) was developed and investigated. The graphite–cellulose acetate system was employed as the basic ink system, which could be easily printed onto the ploy(vinyl chloride) (PVC) substrate. With the natural viscosity and high conductivity of OPPF, the screen-printed electrode (SPE) from the OPPF modified ink exhibited very attractive properties, such as high stability and electrochemical reactivity, low background current and wide electrochemical window. Furthermore, the electrode possessed excellent electrocatalytic activity for the oxidation of dopamine. The linear range for the determination of dopamine was from 1.0 μM to 2.5 mM and the detection limit was 0.5 μM.     

Novel poly (neutral red) nanowires as a sensitive electrochemical biosensing platform for hydrogen peroxide determination

Poly (neutral red) nanowires (PNRNWs) have been synthesized for the first time by the method of cyclic voltammetric electrodeposition using porous anodic aluminum oxide (AAO) template and were examined by scanning electron microscopy (SEM) and transmission electron microscope (TEM). Moreover, horseradish peroxidase (HRP) was encapsulated in situ in PNRNWs (denoted as PNRNWs–HRP) by electrochemical copolymerization for potential biosensor applications. The PNRNWs showed excellent efficiency of electron transfer between the HRP and the glassy carbon (GC) electrode for the reduction of H₂O₂ and the PNRNWs–HRP modified GC electrode showed to be excellent amperometric sensors for H₂O₂ at −0.1 V with a linear response range of 1 μM to 8 mM with a correlation coefficient of 0.996. The detection limit (S/N = 3) and the response time were determined to be 1 μM and <5 s and the high sensitivity is up to 318 μA mM⁻¹ cm⁻².     

A novel biomimetic logic gate for sensitive and selective detection of Pb(II) base on porous alumina nanochannels

A novel biomimetic logic gate sensor for Pb^2 + is established using porous alumina membrane nanochannels modified with morpholino and DNA. It is based on electrochemical detection, and the current response from the diffusion flux of Fe(CN)₆^3 − is influenced by the steric blockage and charge repulsion in nanochannels. A limit of detection (0.1 nM) and good linear range (0.1 nM–5 μM) for Pb^2 + analysis are achieved in the tenth cycle. The sensing strategy shows prospective application in drug release, artificial ion channels, DNA logic gates for controlling biomolecule, and ion translocation.     

Effect of sonication on polymeric membranes

This article studies the effect of 47 kHz ultrasonic (US) waves on polymeric membranes immersed in an aqueous bath. The membranes under study are made from three different polymers: polyethersulfone (PES), polyvinylidenefluoride (PVDF) and polyacrylonitrile (PAN) and present various molecular weight cut-off (MWCO). The evolution of the polymeric structure exposed to US was followed by the measurement of the water permeability and the A_k/Δx parameter which represents the ratio of surface porosity to thickness. Results showed that important variations occurred on certain membranes after irradiation. In addition, microscopic imaging using field emission electron scanning microscopy (FESEM) was performed on irradiated membranes in order to visualize the nature of the degradation. An image analysis method gives the evolution of the pore density, porosity and pore size distribution of a homogeneous area of this membrane before and after irradiation.It has been shown that, over the three materials tested, only the PES is affected by the ultrasonic treatment over all its surface, whereas the others present no significant change in the measured parameters except the PAN (50 kDa) and PVDF (40 kDa) membranes whose edges are affected. In conclusion, in spite of their great efficiency in enhancing filtration processes, ultrasonic waves have to be used with care as the polymeric material itself is sensitive to the ultrasonic waves at the chosen frequency.     

A microtubular all CNT gas diffusion electrode

We report a microtubular gas diffusion electrodes made of multi-walled carbon nanotubes (MWCNT). The electrodes were prepared by inside-out cake filtration of an aqueous MWCNT suspension onto a microfiltration hollow fiber (HF) membrane, followed by washing out the surfactant, drying and removal of the all CNT microtube from the HF membrane. Length, outer diameter, and wall thickness of the tubular electrodes are: up to 44 cm, ~ 1.7 mm and 275 μm, respectively. The BET surface area is 200 m²/g with a porosity of 48–67% and an electrical conductivity of ~ 20 S/cm. Application of this microtubular Gas Diffusion Electrodes (GDE) was studied for the oxygen reduction reaction (ORR) in divided and undivided electrochemical cells. Oxygen supply into the lumen of the tubular electrodes resulted in much higher current densities for ORR than in experiments where the electrolyte was saturated by bubbling with pure oxygen. Within the 0.25–1.0 bar pressure (gauge) region, higher ORR rates were achieved at lower pressure. We also show that H₂O₂ production is possible using the new GDE. We propose to use such novel electrodes for the fabrication of tubular electrochemical reactors, e.g. fuel cells, H₂O₂ generators, CO₂ reduction and other processes that involve GDE application.     

Scanning electrochemical microscopy investigation of the rate of formation of a passivating TiO2 layer on a Ti G4 dental implant

Titanium and alloys with titanium as the major component are widely used for making biomedical implants, such as artificial dental roots. In our laboratory, we have studied the kinetics of the self-healing reaction of the TiO₂ film that forms on the surface of such an implant. Amperometric SECM approach curves were recorded over the surface of a grade 4 titanium (Ti G4) dental implant sample at specific times after the metal surface had been exposed to an air-saturated buffer solution. A ferrocene methanol redox mediator and a platinum microelectrode tip (r = 12.5 μm) were used in the experiments. The effective rate coefficient (k_eff) values for the mediator regenerating surface reaction were estimated using Wittstock's method from the approach curves recorded at different time points. Decreasing values of k_eff over time indicated an increasing rate of formation of the passivating TiO₂ film.     

Nanorods of transition metal oxalates: A versatile route to the oxide nanoparticles

A versatile route has been explored for the synthesis of nanorods of transition metal (Cu, Ni, Mn, Zn, Co and Fe) oxalates using reverse micelles. Transmission electron microscopy shows that the as-prepared nanorods of nickel and copper oxalates have diameter of 250 nm and 130 nm while the length is of the order of 2.5 μm and 480 nm, respectively. The aspect ratio of the nanorods of copper oxalate could be modified by changing the solvent. The average dimensions of manganese, zinc and cobalt oxalate nanorods were 100 μm, 120 μm and 300 nm, respectively, in diameter and 2.5 μm, 600 nm and 6.5 μm, respectively, in length. The aspect ratio of the cobalt oxalate nanorods could be modified by controlling the temperature.The nanorods of metal (Cu, Ni, Mn, Zn, Co and Fe) oxalates were found to be suitable precursors to obtain a variety of transition metal oxide nanoparticles. Our studies show that the grain size of CuO nanoparticles is highly dependent on the nature of non-polar solvent used to initially synthesize the oxalate rods. All the commonly known manganese oxides could be obtained as pure phases from the single manganese oxalate precursor by decomposing in different atmospheres (air, vacuum or nitrogen). The ZnO nanoparticles obtained from zinc oxalate rods are ～55 nm in diameter. Oxides with different morphology, Fe₃O₄ nanoparticles faceted (cuboidal) and Fe₂O₃ nanoparticles (spherical) could be obtained.     

Factors affecting membrane fouling reduction by surface modification and backpulsing

Several factors affecting microfiltration membrane fouling and cleaning, including backpulsing, crossflushing, backwashing, particle size, membrane surface chemistry, and ionic strength, were investigated with suspensions of latex beads. Approximately two-fold permeate volume enhancements over 1 h of filtration were obtained by using water or gas backpulsing, and 50% enhancement was obtained with crossflushing, for filtration of 1.0 μm diameter carboxylate modified latex (CML) particles using unmodified polypropylene (PP) membranes of 0.3 μm nominal pore diameter. When 0.2 μm diameter CML particles or mixtures of 1.0 and 0.2 μm CML particles were used, however, the average flux decreased 60% compared with using 1.0 μm CML particles for experiments with or without backpulsing.PP membranes were rendered hydrophilic with neutral or positively on negatively charged surfaces by grafting monomers of poly(ethylene glycol 200) monomethacrylate (PEG200MA), dimethyl aminoethyl methacrylate (DMAEMA), or acrylic acid (AA), respectively, to the base PP membranes. Filtration experiments show that fouling is not strongly dependent on membrane surface chemistry for filtration of 1.0 μm CML particles without backpulsing. With backpulsing, however, a 10% increase and a 20% decrease of permeate volumes collected in 1 h were observed when the CML particles and the membranes had like charges and opposite charges, respectively, compared to the permeate collected with the unmodified membrane. Using the PP membranes modified with AA, permeate volumes with backpulsing decreased 30 and 40% when NaCl concentrations of 0.01 and 0.1 M, respectively, were added to the feed. However, the permeate volumes did not vary significantly with changing ionic strength for filtration without backpulsing.     

Preparation process for improving cathode electrode structure in direct methanol fuel cell

The cathode electrode structure of the direct methanol fuel cell (DMFC) was improved by a novel catalyst ink preparation method. Regulation of the solvent polarity in the cathode catalyst ink caused increases in the electrochemical active surface (EAS) for the oxygen reduction reaction (ORR) as well as decreases in the methanol crossover effect. In a two-step preparation, agglomerates consisting of catalyst and Nafion ionomers were decreased in size, and polar groups in the ionomers formed organized networks in the cathode catalyst layer. Despite Pt catalysts in the cathode being only 0.5 mg cm^? 2, the maximum power density of the improved membrane electrode assembly (MEA) was 120 mW cm^? 2, at 3 M methanol, which was much larger than that of traditional MEA (67 mW cm^? 2).     

Electrochemical synthesis of Au/polyaniline–poly(4-styrenesulfonate) hybrid nanoarray for sensitive biosensor design

Au/polyaniline (PANI)–poly(4-styrenesulfonate) (PSS) hybrid nanoarray is fabricated for biomolecular sensing in neutral aqueous solutions. Firstly, an array of one-dimensional Au nanorods (diameter = ca. 200 nm, length = ca. 3 μm) is formed by a template-electrodeposition method using a porous anodic alumina membrane, and then a thin PANI–PSS composite layer is electropolymerized on the surface of the Au nanorods. The resulting Au/PANI–PSS hybrid nanoarray exhibits a quasi-reversible redox electrochemical process at ca. +0.11 V and electrocatalytic oxidation of reduced β-nicotinamide adenine dinucleotide (NADH) is attained with a detection limit of 0.3 μM in a neutral solution.     

Looking glass inhibitors: both enantiomeric N-benzyl derivatives of 1,4-dideoxy-1,4-imino-d-lyxitol [a potent competitive inhibitor of α-d-galactosidase] and of 1,4-dideoxy-1,4-imino-l-lyxitol [a weak competitive inhibitor of α-d-galactosidase] inhibit naringinase,an α-l-rhamnosidase competitively

Benzhydryl protection by diphenyldiazomethane of an alcohol in enantiomeric base-sensitive ribonolactones allows short efficient syntheses of 1,4-dideoxy-1,4-imino-d-lyxitol (DIL) and of 1,4-dideoxy-1,4-imino-l-lyxitol (LIL). DIL showed potent [K_i = 0.13 μM]—and LIL showed weak [K_i = 113 μM]—competitive inhibition of α-d-galactosidase. Both enantiomers N-benzyl-DIL [K_i = 64 μM] and N-benzyl-LIL [K_i = 13 μM] were moderate competitive inhibitors of naringinase, an α-l-rhamnosidase.     

Investigation of the CO oxidation rate oscillations using electrochemical promotion of catalysis over sputtered-Pt films interfaced with YSZ

The oscillatory behaviour of CO oxidation was studied at 250 °C and atmospheric pressure using an electrochemical catalyst composed of a thin (60 nm) sputtered-Pt film interfaced with an yttria-stabilized zirconia membrane. Oscillations of CO oxidation rate showed a perfect correlation with those of the electrochemical potential values. Electrochemical promotion of catalysis was used to initiate and stop the oscillatory behaviour. Small current application induced a permanent effect on the oscillatory behaviours. An extremely small negative current (? 17 μA) led to a 4-fold increase of the catalytic activity and created oscillations that were stable even after current interruption. This permanent effect in the oscillatory behaviour of CO oxidation rate is observed for the first time using EPOC. This has been interpreted by the higher tendency of the nanometric-Pt particles to form PtO_x in thin sputtered films.     

Surface structures and electrochemical characteristics of surface-modified carbon anodes for lithium ion battery

Petroleum coke and those heat-treated at 1860 °C, 2100 °C, 2300 °C 2600 °C and 2800 °C (abbreviated as PC, PC1860, PC2100, PC2300, PC2600 and PC2800) were fluorinated by elemental fluorine of 3 × 10⁴ Pa at 200 °C and 300 °C for 2 min. Natural graphite powder samples with average particle sizes of 5 μm, 10 μm and 15 μm (abbreviated as NG5μm, NG10μm and NG15μm) were also fluorinated by ClF₃ of 3 × 10⁴ Pa at 200 °C and 300 °C for 2 min. Transmission electron microscopic (TEM) observation revealed that closed edge of PC2800 was destroyed and opened by surface fluorination, which increased the first coulombic efficiencies of PC2300, PC2600 and PC2800 by 12.1–18.2% at 60 mA/g and by 13.3–25.8% at 150 mA/g in 1 mol/dm³ LiClO₄–ethylene carbonate (EC)/diethyl carbonate (DEC) (1:1 in volume). Light fluorination of NG10μm and NG15μm increased the first coulombic efficiencies by 22.1–28.4% at 150 mA/g in 1 mol/dm³ LiClO₄–EC/DEC/PC (PC: propylene carbonate, 1:1:1 in volume).     

Dual-signal anodic stripping voltammetric determination of trace arsenic(III) at a glassy carbon electrode modified with internal-electrolysis deposited gold nanoparticles

A glassy carbon electrode (GCE) modified with internal-electrolysis deposited gold nanoparticles (AuNPs_ied) was applied to sensitively and selectively detect As(III) by anodic stripping linear sweep voltammetry (ASLSV). The AuNPs_ied/GCE was prepared based on the redox replacement reaction between a supporting-electrolyte-free aqueous HAuCl₄ and a copper sheet in saturated KCl separated by a salt bridge. Under optimum conditions (0.5 M aqueous H₂SO₄, 300-s preconcentration at − 0.4 V), the ASLSV peak current for the As(0)–As(III) oxidation responded linearly to As(III) concentration from 0.02 to 3 μM with a limit of detection (LOD) of 0.9 nM (0.07 μg L^− 1) (S/N = 3), while that for the As(III)–As(V) oxidation was linear with As(III) concentration from 0.02 to 1 μM with a LOD of 4 nM (0.3 μg L^− 1) (S/N = 3). An appropriate high-scan-rate for ASLSV can enhance both the sensitivity and signal-to-noise ratio. This method was applied for analyses of As(III) in real water samples.