Making the practically impossible “Merely difficult”—Cryogenic FIB lift‐out for “Damage free” soft matter imaging

The preparation of thinned lamellae from bulk samples for transmission electron microscopy (TEM) analysis has been possible in the focussed ion beam scanning electron microscope (FIB‐SEM) for over 20 years via the in situ lift‐out method. Lift‐out offers a fast and site specific preparation method for TEM analysis, typically in the field of materials science. More recently it has been applied to a low‐water content biological sample (Rubino 2012). This work presents the successful lift‐out of high‐water content lamellae, under cryogenic conditions (cryo‐FIB lift‐out) and using a nanomanipulator retaining its full range of motion, which are advances on the work previously done by Rubino (2012). Strategies are explored for maintaining cryogenic conditions, grid attachment using cryo‐condensation of water and protection of the lamella when transferring to the TEM. Microsc. Res. Tech. 79:298–303, 2016. © 2016 Wiley Periodicals, Inc.     

In situ TEM studies of micron‐sized all‐solid‐state fluoride ion batteries: Preparation,prospects, and challenges

Trustworthy preparation and contacting of micron‐sized batteries is an essential task to enable reliable in situ TEM studies during electrochemical biasing. Some of the challenges and solutions for the preparation of all‐solid‐state batteries for in situ TEM electrochemical studies are discussed using an optimized focused ion beam (FIB) approach. In particular redeposition, resistivity, porosity of the electrodes/electrolyte and leakage current are addressed. Overcoming these challenges, an all‐solid‐state fluoride ion battery has been prepared as a model system for in situ TEM electrochemical biasing studies and first results on a Bi/La_0.9Ba_0.1F_2.9 half‐cell are presented. Microsc. Res. Tech. 79:615–624, 2016. © 2016 Wiley Periodicals, Inc.     

Derivation of finite element formulation for electrochemical governing equations of ionic polymer actuators

Ionic polymer actuators have recently attracted a great deal of interest as electroactive materials with potentials as soft actuators, sensors, artificial muscles, robotics, and microelectromechanical systems because of their numerous advantages, including low voltage requirement, high compliance, lightness, and flexibility. The platinum-plated Nafion, a perfluorosulfonic acid membrane made by Dupont, is commonly used as a polyelectrolyte in actuator applications. The bending of the ionic polymer actuators in an electric field is dominated by the electro-osmosis of hydrated ions and slow diffusion of free water molecules. The changes in hydration cause a local volumetric strain resulting in bending deformation, such as expansion and contraction. In this study, a two-dimensional finite element (FE) formulation based on the Galerkin method is derived for the governing equations describing these electrochemical responses. In addition, a three-dimensional FE deformation analysis is conducted on the bending behaviors of the platinum-plated ionic polymer actuators. Several numerical studies for ionic polymer actuators, such as plates with various electrode arrangements and disk models in electric field, are performed to confirm the validity of the proposed formulation.     

PVC Membrane Sensor for Potentiometric Determination of Atropine in Some Pharmaceutical Formulations

Abstract

The construction and general performance of a novel potentiometric membrane sensor for determination of atropine has been developed. It is based on the formation of the ion association complex of the atropinium cation with phosphotungstate counter anion as electroactive material dispersed in a PVC matrix, β‐Cyclodextrin and o‐nitrophenyl octyl ether serve as a plasticizer. The sensor shows a fast, stable, near Nernstian response for 1×10^?2 M to 1×10^?6 M atropine at 25°C over the pH range of 3–8 with a cationic slope of 51±0.5 mV/decade. The lower detection limit is 8×10^?7 M and the response time is 20–45 sec. Selectivity coefficients of atropine, relative to a number of interfering substances, were investigated. There are negligible interferences caused by most of the studied cations, anions, and pharmaceutical excipients. The direct determination of atropine shows an average recovery of 98.6% and a mean relative standard deviation (RSD) of 1.6% at 100 µg/mL. The results obtained by determination of atropine in some formulations (atropine injection and eye drops) are favorably comparable with those obtained by the British Pharmacopoeia method. The developed membrane electrode has been used as end point indicator electrode for some potentiometric titrations.     

A spectroscopic proton-exchange membrane fuel cell test setup allowing fluorescence x-ray absorption spectroscopy measurements during state-of-the-art cell tests

A test setup for membrane-electrode-assemblies (MEAs) of proton exchange membrane fuel cells which allows in situ fluorescence x-ray absorption spectroscopy studies of one electrode with safe exclusion of contributions from the counter electrode is described. Interference by the counter electrode is excluded by a geometry including a small angle of incidence (< 6°) between primary beam and electrode layer. The cell has been constructed by introducing just minor modifications to an electrochemical state-of-the-art MEA test setup, which ensures realistic electrochemical test conditions. This is at the expense of significant intensity losses in the path of the incident beam, which calls for the brilliance of third-generation synchrotrons to provide meaningful data. In measurements on Pt∕C and Pt-Co∕C cathodes combined with Pt-C anodes (H(2)/O(2) feed), good data quality was demonstrated both for the majority element Pt as well as for Co despite of a low areal Co density in the order of 0.02 mg/cm(2).     

Analytical Performance of CE Microchips with Amperometric Detection

Abstract

Miniaturized Total Analysis Systems (µTAS), such as microchip electrophoresis devices are promising tools for analytical purposes. Capillary electrophoresis (CE) microchips made of various materials, e.g., poly(methylmethacrylate) (PMMA). Topas (thermoplastic olefin polymer of amorphous structure), and glass have been evaluated in this work. An electrochemical detection that combines adequately with these polymeric and glass microchips has been employed. The performance of amperometric detectors based on an end‐channel configuration was tested. Thus, integration and alignment of gold/platinum wire and thick‐film (screen‐printed carbon electrodes) working electrodes was studied. In order to verify the correct alignment of the end‐channel metal‐wire detector, a gold‐based dual electrode detector was also employed. The dual detector was based on a gold film within the separation channel and a gold wire at the end of the channel. The microchip pretreatment, which can affect the charge on the channel surface and electroosmotic flow (EOF), has been discussed, as well as the separation and injection performance.     

Study on the c-axis preferred orientation of ZnO film on various metal electrodes

ZnO thin film was deposited on various metal electrodes by reactive sputtering, and c-axis preferred orientation of the film has been studied. ZnO, which has high piezoelectricity, is promising for oscillators or filter devices such as surface acoustic wave (SAW) device, gas sensor, and film bulk acoustic resonator (FBAR). But, for the application of ZnO film for these devices, the film should be grown with c-axis normal to the electrode. In this study, Pt, Al, and Au were deposited on Si wafer, and the surface roughness and crystal structure of the ZnO film on the electrode were investigated using AFM, scanning electron microscopy (SEM), and X-ray diffraction (XRD). Columnar structures of ZnO films were grown with c-axis normal to all electrodes, and among them Pt electrode showed the highest preferred orientation of ZnO film.     

In situ,atomic scale observation of electrode topography and reactions

The topographical changes occurring on a Au(111) electrode during simple electrochemical reactions have been followed with an STM capable of operating in situ, i.e. in the electrochemical environment, and of yielding atomic scale resolution. Changes in the surface structure induced by adsorption and desorption of Cl^? ions could be observed and the effects of subjecting the sample to an oxidation-reduction cycle could be monitored.     

An amperometric glucose biosensor based on a screen-printed electrode and Os-complex mediator for flow injection analysis

An amperometric Os-complex mediated glucose biosensor based on a three electrodes planar configuration was constructed using screen printing technique for flow injection analysis. The electrochemical characteristic of the amperometric biosensor was evaluated by the cyclic voltammetry in the absence and presence of Os-complex mediator. The Os-complex mediated biosensor was found to have a C–V curve close to an ideal. The applied potential of the biosensor had been explored and −0.1 V vs. Ag|AgCl reference electrode was selected for avoiding excessive interference from other electroactive species. The biosensor also indicated good stability of more than 90% of its original activity for about 14 months stored at 4 °C. The biosensor on the detection of glucose showed a linear response range of 0.5–30 mM and the correlation coefficient up to 0.99 together with a FIA system. The coefficient of variation was 3.3% for injections with a single biosensor (n = 12). The results show that the biosensor has fast response, good sensitivity and reproducibility for flow injection analysis.     

Electrical and electrochemical properties of the MEH–PPV and MEH–PPV doped calix[4]arene derivative layers for the detection of Cu and Na ions

A modified ITO electrode based on conducting polymer (MEH–PPV) matrix doped with the calix[4]arene molecules (β-ketoimine calix[4]arene) is deposited by spin coating. The carrier transport mechanism of the MEH–PPV and MEH–PPV:β-ketoiminecalix[4]arene films is investigated by using I–V characteristics measurements. The conduction mechanisms in these thin films are identified to be a space-charge-limited current (SCLC). The dielectric behavior of the MEH–PPV and the composite β-ketoimine calix[4]arene/MEH–PPV thin films are investigated by impedance spectroscopy (IS). The Cole–Cole plots are studied showing single semicircles and the solid interfaces are modeled by an equivalent circuit. The characteristics of chemical sensors based on MEH–PPV and MEH–PPV doped β-ketoimine calix[4]arene thin films for the detection of Cu²⁺ and Na⁺ ions are investigated by electrochemical impedance spectroscopy (EIS). The experimental impedance data of the modified electrodes are modeled by an equivalent circuit using the Z-View software. The inclusion of calixarene molecules into conducting polymer (MEH–PPV) exhibited considerable rise charge transfer resistance and improves sensing properties.     

Analysis of 2-Benzo[c]cinnoline Nanofilm at the Gold Surface

Abstract

A polycrystalline gold surface was modified with 2-benzo[c]cinnoline (BCC) in nonaqueous media using cyclic voltammetry. A multilayer BCC nanofilm at the gold surface was formed by the electrochemical reduction of 2-benzo[c]cinnoline diazonium salt (BCC-DAS). Grafting of BCC molecules onto the gold surface was verified by cyclic voltammetry using various redox probes, electrochemical impedance spectroscopy, and Raman spectroscopy. The BCC film thickness was measured by ellipsometry and calculated as 46 nm indicating a multilayer film formation. The stability and the potential range of the novel Au-BCC modified electrode were also studied in open atmosphere and pure water. The working potential range of Au-BCC electrode was found to be between ?1.8 and +1.6 V.     

Electrochemical Behavior of Uric Acid at a Meso‐2,3‐Dimercaptosuccinic Acid Self‐Assembled Gold Electrode

Abstract

The fabrication and electrochemical characteristics of a meso‐2,3‐dimercaptosuccinic acid (DMSA) self‐assembled monolayer modified gold electrode were investigated. The DMSA self‐assembled electrode can enhance the electrochemical stability of uric acid (UA) and the electrochemical reaction of UA on the DMSA electrode has been studied by cyclic voltammetry and electrochemical quartz crystal microbalance. Some electrochemical parameters, such as diffusion coefficient, standard rate constant, electron transfer coefficient, and protons transfer number have been determined for the electrochemical behavior on the DMSA self‐assembled monolayer electrode. The electrode reaction of UA is an irreversible process which is controlled by the diffusion of UA with two electrons and two protons transfer at the DMSA/Au electrode. In phosphate buffer (pH 5.0), the peak current is proportional to the concentration of UA in the range of 8.0×10^?5?1.0×10^?2 mol L^?1 and 8.0×10^?5?8.0×10^?3 mol L^?1 for the cyclic voltammetry and differential pulse voltammetry methods with the detection limits of 1×10^?6 and 8×10^?7 mol L^?1, respectively. This method can be applied to the determination of the UA concentration.     

A polyaniline based intrinsically conducting coating for corrosion protection of structural steels

Among the various corrosion protection strategies for structural steels, coating techniques provide the most cost‐effective protection and have been used as the primary mode of corrosion protection. Existing coating techniques however have been used mainly for their barrier capability and therefore all have a limited service life due to oxidation aging, electrolytic degradation, or various inadvertent defects and flaws occurred in and after coating applications. This work investigated the anti‐corrosion potential of a π‐conjugated polymer—polyaniline (PANi), which was doped into an intrinsically conducting polymer and then included in a two‐layer coating system as a primer layer. To achieve a long service life, the primer layer was made by mixing the conductive PANi in a waterborne poly‐vinyl butyral solution to provide strong adhesion to steel surface, and then topcoated with a layer of elastomer‐modified polyethylene to obtain extra mechanical and barrier protections. Two ASTM standard tests were conducted to evaluate the corrosion durability and tensile adhesion of the two‐layer system, in which the system demonstrated superior performance. The Scanning Kelvin Probe Force Microscopy (SKPFM) was used to provide the microscopic evidences for the outstanding performance. Microsc. Res. Tech. 76:1186–1195, 2013. © 2013 Wiley Periodicals, Inc.     

Combining Ar ion milling with FIB lift-out techniques to prepare high quality site-specific TEM samples

Focused ion beam (FIB) techniques can prepare site‐specific transmission electron microscopy (TEM) cross‐section samples very quickly but they suffer from beam damage by the high energy Ga⁺ ion beam. An amorphous layer about 20–30 nm thick on each side of the TEM lamella and the supporting carbon film makes FIB‐prepared samples inferior to the traditional Ar⁺ thinned samples for some investigations such as high resolution transmission electron microscopy (HRTEM) and electron energy loss spectroscopy (EELS). We have developed techniques to combine broad argon ion milling with focused ion beam lift‐out methods to prepare high‐quality site‐specific TEM cross‐section samples. Site‐specific TEM cross‐sections were prepared by FIB and lifted out using a Narishige micromanipulator onto a half copper‐grid coated with carbon film. Pt deposition by FIB was used to bond the lamellae to the Cu grid, then the coating carbon film was removed and the sample on the bare Cu grid was polished by the usual broad beam Ar⁺ milling. By doing so, the thickness of the surface amorphous layers is reduced substantially and the sample quality for TEM observation is as good as the traditional Ar⁺ milled samples.     

Electrochemical behaviors of benzoic acid at polyaniline/CuGeO3 nanowire modified glassy carbon electrode

20 wt.% polyaniline/CuGeO₃ nanowires have been used as glassy carbon electrode (GCE) modified materials for electrochemical determination of benzoic acid (BA) in neutral solution. The intensities of the anodic cyclic voltammogram (CV) peaks increase linearly with the increase of BA concentration and scan rate. The linear range is 0.001–2 mM and detection limit is 0.96 μM and 0.47 μM for cvp1 and cvp2, respectively at a signal-to-noise ratio of 3. 20 wt.% polyaniline/CuGeO₃ nanowire modified GCE exhibits good stability and reproducibility. Polyaniline plays an important role in the electrochemical responses of BA at polyaniline/CuGeO₃ nanowire modified GCE. The detection limit decreases to 0.64 μM and 0.28 μM for cvp1 and cvp2, respectively with the polyaniline content increasing to 40 wt.%. Polyaniline/CuGeO₃ nanowire modified GCE exhibit better electrochemical performance than traditional methods.     

Focused ion beam milling of vitreous water: prospects for an alternative to cryo-ultramicrotomy of frozen-hydrated biological samples

The feasibility of using a focused ion beam (FIB) for the purpose of thinning vitreously frozen biological specimens for transmission electron microscopy (TEM) was explored. A concern was whether heat transfer beyond the direct ion interaction layer might devitrify the ice. To test this possibility, we milled vitreously frozen water on a standard TEM grid with a 30‐keV Ga⁺ beam, and cryo‐transferred the grid to a TEM for examination. Following FIB milling of the vitreous ice from a thickness of approximately 1200 nm to 200–150 nm, changes characteristic of heat‐induced devitrification were not observed by TEM, in either images or diffraction patterns. Although numerous technical challenges remain, it is anticipated that ‘cryo‐FIB thinning’ of bulk frozen‐hydratred material will be capable of producing specimens for TEM cryo‐tomography with much greater efficiency than cryo‐ultramicrotomy, and without the specimen distortions and handling difficulties of the latter.     

Analysis of effect of nanoporous alumina substrate coated with polypyrrole nanowire on cell morphology based on AFM topography

In this study, in situ electrochemical synthesis of polypyrrole nanowires with nanoporous alumina template was described. The formation of highly ordered porous alumina substrate was demonstrated with Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM). In addition, Fourier transform infrared analysis confirmed that polypyrrole (PP) nanowires were synthesized by direct electrochemical oxidation of pyrrole. HeLa cancer cells and HMCF normal cells were immobilized on the polypyrrole nanowires/nanoporous alumina substrates to determine the effects of the substrate on the cell morphology, adhesion and proliferation as well as the biocompatibility of the substrate. Cell adhesion and proliferation were characterized using a standard MTT assay. The effects of the polypyrrole nanowires/nanoporous alumina substrate on the cell morphology were studied by AFM. The nanoporous alumina coated with polypyrrole nanowires was found to exhibit better cell adhesion and proliferation than polystyrene petridish, aluminum foil, 1st anodized and uncoated 2nd anodized alumina substrate. This study showed the potential of the polypyrrole nanowires/nanoporous alumina substrate as biocompatibility electroactive polymer substrate for both healthy and cancer cell cultures applications.     

Determination of diffusion controlled reaction rates at a solid/liquid interface using scanning electron microscopy

A high‐resolution method has been developed for the determination of localized values of interfacial reaction rate and mass transfer coefficient in aqueous solution. Scanning electron microscopy has been successfully applied to this problem through the measurement of electroplated film thickness formed under limiting current conditions. The method involves the calculation of local values of reaction rate via Faraday's laws and subsequent conversion of the data to absolute values of mass transfer coefficient. The technique has been verified in an undisturbed, turbulent flow regime (rotating cylinder electrode) through the use of Sherwood group dimensionless analysis. The resulting relationship shows comparable accuracy relative to electrochemical measurements. Favourable comparison has also been made with the generally accepted rotating cylinder correlation of Eisenberg, Tobias and Wilke. Differential rates of mass transfer to a single surface under conditions of disturbed flow have also been examined at a high spatial resolution using the stepped rotating cylinder electrode geometry. In this case, reaction rates have been measured as a function of circumferential distance within a recirculation zone situated immediately downstream of a backward‐facing step.     

A Low Cost‐Computer‐Controlled and Powered Multichannel Potentiostat for General Use in Development of Inexpensive Electrochemical Sensors

Abstract

Described herein, is an inexpensive 16‐channel potentiostat that is both controlled and powered by a PC multifunction data acquisition card. As an enabling example, the potentiostat was used to measure the extent for which insoluble manganese oxide powder will pre‐oxidize ascorbic acid in a phosphate buffered saline solution. This technique to reduce electroactive interferent species has recently been reported to be useful for enzyme‐based electrochemical sensors. Under the conditions studied, it was found that manganese oxide reduces both hydrogen peroxide and ascorbic acid to 20.6% and 27.2% of their original signal strength respectively. With another 4 minutes of exposure to the oxide, signals due to hydrogen peroxide and ascorbic acid dropped to 9.0% and 5.0%, respectively.     

基于自组装分子印迹膜的胆固醇电化学传感器

基于自组装技术在丝网印金电极表面制备分子印迹膜,研制胆固醇电化学仿生传感器.采用循环伏安分析法对电极修饰过程的电化学特性进行表征,采用计时电流法对胆固醇传感器的浓度响应特性进行检测.将传感器对0～700 nM不同浓度胆固醇进行检测,线性范围为100～700 nM,灵敏度为-2.4 nA/nM.