Imaging the Origins of Coating Degradation and Blistering Caused by Electrolyte Immersion Assisted by SECM

A new method to image the origins of coating degradation and the nucleation and subsequent growth of blisters by using SECM in the feedback mode is proposed. The unique role of chloride ions towards coating performance has been established at a very early stage following immersion of the sample. We believe this to show the earlier stages of blistering in a coated metal system ever recorded. The method allowed for the first time to detect the nucleation and to monitor quantitatively the growth process of an individual blister, because it effectively advanced towards the microelectrode when scanned at constant height over the sample.     

Poly[N‐isopropyl acrylamide]‐co‐polyurethane copolymers for controlled release of urea

A novel block copolymer of poly[N‐isopropyl acrylamide]‐co‐polyurethane was designed, synthesized, and applied as controlled release fertilizer coating. Structural confirmation of the copolymer was performed using FTIR and ¹H‐NMR spectra and elemental analysis. The coating process consists essentially of immersing urea granules in molten polymer and removing the coated urea from the melt by centrifugal action. The morphology of the coated urea was studied using scanning electron microscope (SEM). The polymer coat of the urea granules was found to swell in water forming pores and enabling the release of urea. The urea released from the granule, monitored using a mass spectroscopy technique, was found to be governed by pH of the aqueous medium. The study anticipates development of a beneficiary fertilizer coat in terms of improving controlled release over a period of time which can be tailored by soil temperature, pH and moisture. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3236–3243, 2010     

Nafion-CNT coated carbon-fiber microelectrodes for enhanced detection of adenosine

Adenosine is a neuromodulator that regulates neurotransmission. Adenosine can be monitored using fast-scan cyclic voltammetry at carbon-fiber microelectrodes and ATP is a possible interferent in vivo because the electroactive moiety, adenine, is the same for both molecules. In this study, we investigated carbon-fiber microelectrodes coated with Nafion and carbon nanotubes (CNTs) to enhance the sensitivity of adenosine and decrease interference by ATP. Electrodes coated in 0.05 mg mL(-1) CNTs in Nafion had a 4.2 ± 0.2 fold increase in current for adenosine, twice as large as for Nafion alone. Nafion-CNT electrodes were 6 times more sensitive to adenosine than ATP. The Nafion-CNT coating did not slow the temporal response of the electrode. Comparing different purine bases shows that the presence of an amine group enhances sensitivity and that purines with carbonyl groups, such as guanine and hypoxanthine, do not have as great an enhancement after Nafion-CNT coating. The ribose group provides additional sensitivity enhancement for adenosine over adenine. The Nafion-CNT modified electrodes exhibited significantly more current for adenosine than ATP in brain slices. Therefore, Nafion-CNT modified electrodes are useful for sensitive, selective detection of adenosine in biological samples.     

Long–term Drifts in Sensitivity Caused by Biofouling of an Amperometric Oxygen Sensor

Changes in oxygen sensitivity of an poly(o‐phenylenediamine) (PoPD) coated gold electrode was determined by constructing calibration curves in vitro. Oxygen sensitivities recorded in the presence of biofoulants were significantly different from those recorded in buffer; however, PoPD demonstrated its effectiveness in providing some resistance to changes in oxygen sensitivity over time compared to a bare electrode. Three sets of PoPD‐coated electrodes were calibrated in simple electrolyte of phosphate buffered saline; each set yielding an average oxygen sensitivity of 0.58±0.03 μA/ppm, 0.68±0.01 μA/ppm, and 0.48±0.01 μA/ppm (n=4), which shows the electrode to electrode variation in the PoPD‐coating/electrode. These sets were correspondingly exposed to bovine serum albumin, fibrinogen, rat brain homogenate. Exposure to these biofoulants resulted in decreases in sensitivity ranging from 26–35 % after immediate exposure. Furthermore, long‐term exposure to some biofoulants causes significant decreases in sensitivity over a time period of 14 days. We also estimated through in vitro exposure to rat brain homogenate the errors that might be associated with current methods of calibration. Sensitivities to oxygen determined by precalibration resulted in a 50 % error from the sensitivity found in vitro; the error from postcalibration after rinsing resulted in 25 % error.     

Iron oxide coated gold nanorods: synthesis, characterization, and magnetic manipulation

We report a simple process to generate iron oxide coated gold nanorods. Gold nanorods, synthesized by our three-step seed mediated protocol, were coated with a layer of polymer, poly(sodium 4-styrenesulfonate). The negatively charged polymer on the nanorod surface electrostatically attracted a mixture of aqueous iron(II) and iron(III) ions. Base-mediated coprecipitation of iron salts was used to form uniform coatings of iron oxide nanoparticles onto the surface of gold nanorods. The magnetic properties were studied using a superconducting quantum interference device (SQUID) magnetometer, which indicated superparamagnetic behavior of the composites. These iron oxide coated gold nanorods were studied for macroscopic magnetic manipulation and were found to be weakly magnetic. For comparison, premade iron oxide nanoparticles, attached to gold nanorods by electrostatic interactions, were also studied. Although control over uniform coating of the nanorods was difficult to achieve, magnetic manipulation was improved in the latter case. The products of both synthetic methods were monitored by UV-vis spectroscopy, zeta potential measurements, and transmission electron microscopy. X-ray photoelectron spectroscopy was used to determine the oxidation state of iron in the gold nanorod-iron oxide composites, which is consistent with Fe2O3 rather than Fe3O4. The simple method of iron oxide coating is general and applicable to different nanoparticles, and it enables magnetic field-assisted ordering of assemblies of nanoparticles for different applications.     

Atomic layer deposition of metal oxides on pristine and functionalized graphene

We investigate atomic layer deposition (ALD) of metal oxide on pristine and functionalized graphene. On pristine graphene, ALD coating can only actively grow on edges and defect sites, where dangling bonds or surface groups react with ALD precursors. This affords a simple method to decorate and probe single defect sites in graphene planes. We used perylene tetracarboxylic acid (PTCA) to functionalize the graphene surface and selectively introduced densely packed surface groups on graphene. Uniform ultrathin ALD coating on PTCA graphene was achieved over a large area. The functionalization method could be used to integrate ultrathin high-kappa dielectrics in future graphene electronics.     

Sol–gel synthesis and characterisation of nanoporous zirconium titanate coated on 316L SS for biomedical applications

In this study, the nanoporous zirconium titanate was prepared using sol–gel process and coated over 316L SS implants via dip-coating technique. XRD patterns of zirconium titanate are crystalline and orthorhombic in structure. FT-IR spectra showed a broad band between 3,500 and 3,300 cm⁻¹, which was assigned to fundamental stretching vibrations of hydroxyl groups. The set of overlapping peaks in the range of 810–520 cm⁻¹ are related to Zr–O and Zr–O–Ti groups. SEM-EDAX and TEM showed the surface morphology of coated zirconium titanate to be porous and uniform. Excellent adhesion of the coating to the substrate has been achieved. The contact angle value was found to be 12°. The coating acts as a barrier layer to the metallic implants and induces the formation of hydroxyapatite layer on the metal surfaces. These results revealed that the nano zirconium titanate coated 316L SS exhibit higher bioactivity compared to that of uncoated 316L SS.     

Efficient and highly reproducible capillary electrophoresis-mass spectrometry of peptides using Polybrene-poly(vinyl sulfonate)-coated capillaries

The potential of capillaries noncovalently coated with a bilayer of oppositely charged polymers for the analysis of peptides by CE-MS was investigated. Bilayer coatings were produced by subsequently rinsing fused-silica capillaries with a solution of Polybrene (PB) and poly(vinyl sulfonate) (PVS). The PB-PVS coating showed to be fully compatible with MS detection causing no ionization suppression or background signals. The bilayer coating provided a considerable EOF at low pH, thereby facilitating the fast separation of peptides using a BGE of formic acid (pH 2.5). Under optimized CE-MS conditions, for enkephalin peptides high separation efficiencies were obtained with plate numbers in the range of 300,000-500,000. It is demonstrated that both the cancellation of the hydrodynamic capillary flow induced by the nebulizer gas and a sufficiently high-data acquisition rate are crucial for achieving these efficiencies. The overall performance of the CE-MS system using PB-PVS-coated capillaries was evaluated by the analysis of a tryptic digest of cytochrome c. The system provided an efficient separation of the peptide mixture, which could be effectively monitored by MS/MS detection allowing identification of at least 13 peptides within a time interval of 1.5 min. In addition, the PB-PVS coating proved to be very consistent yielding stable CE-MS patterns with highly favorable migration time reproducibilities (RSDs < 1% over a 3-day period).     

Individually addressable microelectrode array for monitoring oxygen and nitric oxide release

We have fabricated a six individual addressable gold working electrode microarray. The device is wirebonded to an eight-pin DIL package that can be easily interconnected to an external multi-channel potentiostat. A polyion complex film coating on the electrode surface provides a suitable coating for the growth of cells. The responses of oxygen and nitric oxide were assessed on uncoated and coated devices using electroanalytical methods. The film coating reduced the diffusion current by approximately 20% in both cases. No changes in the electrochemical mechanism were observed. Simultaneous recordings were obtained for 2 h in the presence of the cells, thus the device is stable for the duration of the bioanalytical measurements. Measurements were conducted to study the simultaneous changes in oxygen and nitric oxide levels in cultured fibroblast cells in the presence of growth hormones that cause cell proliferation. Increases in oxygen consumption of the cells were coupled with increases in nitric oxide levels when in the presence of the growth hormones. Use of a biological detergent to cause an oxidative burst resulted in a large increase in the current for potentials set to detect nitric oxide and oxygen.     

PREPARATION OF CHITOSAN COATED METAL AFFINITY CHROMATOGRAPHY ADSORBENT

A new and an inexpensive adsorbent of chitosan coated silica for immobilized metal affinity chromatography(IMAC) was studied.After a double coating,the chitosan coated on silica beads could be up to 53.4mg/g silica beads.When pH&gt;3.8,the metal ligand Cu^2+ was chelated on the coated chitosan with a bound capacity of 14.6mg/g chitosan without introducing iminodiacetic acid(IDA).     

Increasing sensitivity and decreasing spot size using an inexpensive, removable hydrophobic coating for matrix-assisted laser desorption/ionisation plates

Spot size reduction and increased detection sensitivity in matrix-assisted laser desorption/ionisation (MALDI) of small molecules are accomplished by using an inexpensive and removable hydrophobic coating for MALDI targets, based on 3M Scotch Gard surface treatment. Several variations in sample preparation were explored, such as surface coating technique, identity of the matrix, solvent composition, and the type of metal support plate used. These were investigated on both uncoated and coated surfaces and their impact on spot size, crystal coverage, and sensitivity is presented here. Additionally, crystallisation behaviour obtained on coated plates is compared with that on uncoated plates using scanning electron microscope analysis. To demonstrate the potential of the new coating technique, erythromycin A and valinomycin are studied to determine the increase in detection sensitivity of coated plates in comparison to uncoated plates, and to reveal the suitability of the plates for application in combined high-performance liquid chromatography/MALDI (HPLC/MALDI), where widely varying solvent compositions and droplet volumes are observed. It is shown that enhancements in detection sensitivities correlate very well with the achieved spot size reduction. The versatility of the coated plates is also exhibited by the ease of removing the surface layer, after which the plates can be rigorously cleaned without worry about damaging the hydrophobic surface, followed by a quick reapplication of new hydrophobic coating material. This makes the non-polar coating superior to more expensive commercial hydrophobic-coated targets, which are much more delicate to clean. Furthermore, cleaning and reapplication eliminate potential carry-over effects and the easy application procedure also makes the fabrication of inexpensive, disposable MALDI targets readily possible.     

Novel metal‐ion‐mediated,complex‐imprinted solid‐phase microextraction fiber for the selective recognition of thiabendazole in citrus and soil samples

A novel metal‐ion‐mediated complex‐imprinted‐polymer‐coated solid‐phase microextraction (SPME) fiber used to specifically recognize thiabendazole (TBZ) in citrus and soil samples was developed. The complex‐imprinted polymer was introduced as a novel SPME coating using a “complex template” constructed with Cu(II) ions and TBZ. The recognition and enrichment properties of the coating in water were significantly improved based on the metal ion coordination interaction rather than relying on hydrogen bonding interactions that are commonly applied for the molecularly imprinting technique. Several parameters controlling the extraction performance of the complex‐imprinted‐polymer‐coated fiber were investigated including extraction solvent, pH value, extraction time, metal ion species, etc. Furthermore, SPME coupled with HPLC was developed for detection of TBZ, and the methods resulted in good linearity in the range of 10.0–150.0 ng/mL with a detection limit of 2.4 ng/mL. The proposed method was applied to the analysis of TBZ in spiked soil, orange, and lemon with recoveries of 80.0–86.9% and RSDs of 2.0–8.1%. This research provides an example to prepare a desirable water‐compatible and specifically selective SPME coating to extract target molecules from aqueous samples by introducing metal ions as the mediator.     

A comparison of the electrochemical stabilities of metal,polymer and graphite coated nanospray emitters

Chronoamperometry (CA) and cyclic voltammetry (CV) were used to compare the electrochemical behavior of metal, polymer and graphite coated nanospray emitters. It is shown that electrochemical reactions occurring at the emitter surface limit the lifetime of the noble metal coated nanospray emitters while the graphite coated nanospray emitters show good electrochemical stabilities. Although the surface of the graphite coated emitters may be passivated at positive potentials, the conductive coating is not lost as for the noble metal coated nanospray emitters. The graphite coated nanospray emitters still produced a stable nanospray signal despite the presence of a passivated surface. The polymer (i.e. polyaniline) coated nanospray emitters showed very low electrochemical activity and could not be thoroughly tested by CA. The relative short lifetimes seen in the electrochemical tests are qualitatively comparable with those obtained in nanospray experiments, in which only the outmost tip of the emitter is electrochemically active. However, the electrochemical stress during CA far exceeds the stress during ESI, which implies that CA can be used to perform quick and simple estimates of emitter stabilities. To our knowledge, this is the first time the electrochemical behavior of metal, polymer and graphite coated nanospray emitters has been compared.     

Polystyrene film-coated glassware: a new means of reducing metal losses in trace metal speciation

A recently developed process for coating a glass surface with polystyrene (PS) film, by use of a simple chemical process has been used to reduce trace metal adsorption by cell components. The glass coating is a two-step procedure consisting of covalent attachment of vinyl-terminated PS to Si atoms on the glass surface then adsorption of PS from solution to create a stable PS film. To assess the quality of the coating we used anodic stripping voltammetry to study the adsorption of lead and cadmium ions in coated and untreated glass cells. In both short and long-term (24 h) experiments we observed that the amount of metal adsorbed was considerably less for the PS film-coated glass cell than for the uncoated cell. Further experiments showed that metal desorption is faster and metal contamination after cleaning is significantly lower for the coated cells. The PS film was, moreover, stable over a period of 6 months within the pH range 3.5–9.     

Static adsorptive coating of poly(methyl methacrylate) microfluidic chips for extended usage in DNA separations

A simple and robust static adsorptive (dynamic) coating process using 2% hydroxyethylcellulose was developed for surface modification of poly(methyl methacrylate) (PMMA) microfluidic chips for DNA separations, suitable for usage over extended periods, involving hundreds of runs. The coating medium was also used as a sieving matrix for the DNA separations following the coating process. Four consecutive static treatments, by simply filling the PMMA chip channels with sieving matrix once every day, were required for obtaining a stable coating and optimum performance. The performance of the coated chips at different phases of the coating process was studied by consecutive gel electrophoretic separations with LIF detection using a PhiX-174/HaeIII DNA digest sample. The coated chip, with daily renewal of the sieving matrix, showed high stability in performance during a 25-day period of systematic study, involving more than 100 individual runs. The performance of the coated chip also remained almost the same after 3 months of continuous usage, during which over 200 separations were performed. The average precision of migration time for the 603-bp fragment was 1.31% RSD (n = 6) during the 25-day study, with a separation efficiency of 6.5 x 10(4) plates (effective separation length 5.4 cm).     

Evaluating the performance of organic coatings under mechanical stress using electrochemical impedance spectroscopy

Stress in coatings originating from a mechanical load imposed during exploitation is a relatively unexplored field of investigation. Paradoxically, a number of constructions and installations seem to operate under such conditions. The purpose of this work was to investigate the impact of a cyclic mechanical load exerted on coating/metal systems. It was the authors aim to verify whether repeated mechanical stress constitutes a significant factor contributing to coating degradation. Epoxy coated St3SAl steel samples were subjected to 21,000 uniaxial strain/release cycles. The maximum force applied assured maintenance within the elastic deformation region of the metal substrate. The state of the protective film was monitored using electrochemical impedance spectroscopy. The coating response to the mechanical load occurred in a three-stage process. The system subjected to the strain/release cycles revealed signs of degradation earlier compared to a non-strained, reference sample.Contribution to the 3rd Baltic Conference on Electrochemistry GDASK-SOBIESZEWO, 23–26 April 2003.Dedicated to the memory of Harry B. Mark, Jr. (February 28, 1934–March 3rd, 2003)     

Spectroscopic studies of trimetoxypropylsilane and bis(trimethoxysilyl)ethane sol-gel coatings on aluminum and copper

Trimethoxypropylsilane (TMPS) and bis(trimethoxysilyl)ethane (BTMSE) were used as surface modifiers of metal vie the sol-gel process and dip coating. In addition to the single coating of Al, Cu and Sn, double treatments of Al were also conducted by combining coatings with these sol-gels in different sequences. Reflection and absorption infrared spectroscopy (RAIR) was employed to characterize and to trace the proceeding of the sol-gel process of the films. It was found that the silanol condensation occurs in the coating films on Al and the covalent linkage exists between the TMPS film and copper surface. From the assigned vibration modes, two conformers were identified in pure TMPS, TMPS sol-gel and coated film. A series of dip coating experiments with different concentrations of TMPS sol-gel was conducted, and the results from the collected RAIR spectra of the coated samples suggested that the coated Cu consistently has a better RAIR spectrum than that of the coated Al. The TMPS sol-gel appeared to have a better affinity to Cu than to Al. The temperature effect and the aging effect in the coating films were studied. X-ray photoelectronic spectroscopy (XPS) was employed to characterize the coated film, and the XPS data confirm the formation of the siloxane film from the silane coupling agents (SCA). Electrochemical impedance spectra (EIS) have been collected for bare Al and Cu, BTMSE sol-gel coated Al, and TMPS sol-gel coated Cu in 0.15M NaCl solution. The corresponding electronic circuit parameters have been determined to match the experimental EIS data.     

Adsorptive BSA Coating Method for CE to Separate Basic Proteins

A novel and simple coating method was developed by coating bovine serum albumin (BSA) onto the inner surface of a fused-silica capillary, to avoid the adsorption of analytes during CE. The advantage presented here was that the coating process is more simple, fast, stable, and reproducible. The coated capillary avoided the adsorption of analytes onto the inner surface of a fused-silica capillary and might be a promising candidate for separation of complex biological samples with further development. Meanwhile, the efficiencies of the coated capillary were evaluated by EOF, chromatographic peak shape, and theoretical plate number (N m^?1) of RNase A. The optimal coating conditions were obtained from the results. The pH value of coating buffer PB was 4.2, the standing time was 12 h at 4 °C, and the coating concentration of BSA was 1.5 mg mL^?1. The stability of the coating on the inner wall of the capillary and the reproducibility of the coated capillaries were good. The theoretical plate number values of RNase A were over 1.3 × 10⁵ (N m^?1) in the coated capillary. After successive electrophoresis for 48 h using the coated capillary, the RSD values of EOF and the theoretical plate number were 4.14 % and 9.14 %, respectively. In addition, the RSD values of EOF and the theoretical plate number (N m^?1) in the coated capillaries were 13.19 % and 8.96 %, respectively. Finally, the coated capillary was successfully applied to separate the mixture of four basic proteins (RNase A, lysozyme, trypsin and myoglobin).     

Stability of capillaries coated with highly charged polyelectrolyte monolayers and multilayers under various analytical conditions--application to protein analysis

The stability of capillaries coated with highly charged polyelectrolytes under various analytical conditions was studied, as well as their performance for the analysis of proteins by Capillary Electrophoreis (CE) over a wide range of pH (2.5-9.3). In this study, fused silica capillaries were modified either with a poly(diallyldimethylammonium) chloride (PDADMAC) monolayer or PDADMAC/poly(sodium 4-styrenesulfonate) (PSS) multilayer coatings, using optimal coating conditions previously determined. Results show that the coated capillaries are remarkably stable and efficient to limit protein adsorption under a variety of extreme electrophoretic conditions even in the absence of the coating agent in the background electrolyte which is exceptional for non-covalent coatings. Monolayer coated capillaries were demonstrated for the first time to be stable to acidic rinses and to organic solvents which proves that the stability of the capillaries is highly dependent on the coating procedure used. In addition, PDADMAC/PSS multilayer coatings were found to be stable to alkaline treatments. PDADMAC/PSS coated capillaries gave excellent performances for the analysis of proteins covering a large range of pI (4-11) and of molecular weight (14-65 kDa) over a wide pH range (i.e. 2.5-9.3). Even at high pH 9.3, protein analysis was possible with very good repeatabilities (RSD(tm)<1% and RSD(CPA)<2.6% (n ≥ 8)) and high peak efficiencies in the order of 700,000.     

Mapping the distribution of components in formulated polymeric membranes using FTIR-ATR microscopy

This paper shows how FTIR-ATR microscopy can be used to monitor the distribution of components in polymeric membranes without the need for extensive sample preparation. The validity of the technique is proven using a different technique, namely ESEM. Three examples of its use are given; a drug in a pharmaceutical tablet, a biocide in a PVC formulation and a defect on a polymer coated metal.