Atmospheric Pressure Plasma Deposition of Polyfuran

The atmospheric pressure radiofrequency (RF) plasma polymerization of furan was carried out with the objective of synthesizing polyfuran thin film. The structure, compositions and morphology of the plasma deposited polyfuran film were investigated by Fourier transform infrared (FTIR), atomic force microscopy (AFM), ultraviolet‐visible absorption spectroscopy (UV‐vis) and thermogravimetric analysis (TGA). The formation of polyfuran was confirmed using FTIR and UV‐visible analysis. The properties of plasma‐deposited polyfuran were compared with those of chemically synthesized polyfuran. Although the plasma deposited thin film polyfuran shows lower thermal stability than that of chemically synthesized polyfuran. It has better solubility in CHCl₃, also. Thin uniform polyfuran films are obtained in plasma assisted polyfuran deposition, while particles are obtained in chemical polyfuran polymerization.     

Gas flow-field induced director alignment in polymer dispersed liquid crystal microdroplets deposited on a glass substrate

Abstract

Polymer dispersed liquid crystal thin films have been deposited on glass substrates by the processes of polymerization and solvent evaporation induced phase separation. The electron and the optical polarization microscopies of the films reveal that PDLC microdroplets formed during the process of phase separation near the top surface of the film remain exposed and respond to shear stress due to air or gas flow on the surface. Optical response of the film to an air flow-induced shear stress input on the free surface has been measured. Director orientation in the droplets changes with the applied shear stress leading to time varying transmitted light intensity. Director dynamics of the droplet for an applied step shear stress has been discussed from free energy considerations. Results on the measurement of light transmission as a function of the gas flow parameter unambiguously demonstrate the potential of these systems for use as boundary layer and gas flow sensors.     

Enzyme microsensor for glucose with an electrochemically synthesized enzyme-polyaniline film

An enzyme microsensor for glucose was fabricated by the electrochemical polymerization method. A glucose oxidase-entrapped polyaniline (GOD-polyaniline) film was deposited on the top of a platinum fibre (50 μm in diameter) by the electrochemical oxidative polymerization of aniline in a pH 7 buffer solution in the presence of glucose oxidase. The GOD-polyaniline films retained GOD activity and oxygen permeability but prevented large molecules from permeating. Glucose was auperometrically determined with the electrochemically fabricated microsensor in the concentration range 10⁻⁴ to 5 × 10⁻³ M.     

Properties of Dendrimer‐Encapsulated Pt Nanoparticles Doped Polypyrrole Composite Films and Their Electrocatalytic Activity for Glucose Oxidation

A type of novel electroanalytical sensing nanobiocomposite material was prepared by electropolymerization of pyrrole containing poly(amidoamine) dendrimers‐encapsulated platinum nanoparticles (Pt‐PAMAM), and glucose oxidase (GOx). The Pt nanoparticles encapsulated in PAMAM are nearly monodisperse with an average diameter of 3 nm, and they provide electrical conductivity. Polypyrrole acts as a polymer backbone to give stable and homogeneous cast thin films, and it also defines the electrical conductivity. Both Polypyrrole and PAMAM can provide a favorable microenvironment to keep the bioactivity of enzymes such as glucose oxidase. The homogeneity of GOx/Pt‐PAMAM‐PPy nanobiocomposite films was characterized by atomic force microscopy (AFM). Amperometric biosensors fabricated with these materials were characterized electrochemically using cyclic voltammetry (CV), electrochemical impedance spectra (EIS) and amperometric measurements in the presence of hydrogen peroxide or glucose. All those show the resultant biosensor sensitivity was strongly enhanced within the nanobiocomposite film. The optimized glucose biosensor displayed a sensitivity of 164 μA mM^?1 cm^?1, a linear range of 0.2 to 600 μM, a detection limit of 10 nM, and a response time of <3 s.     

Behavior and surface energies of polybenzoxazines formed by polymerization with argon,oxygen, and hydrogen plasmas

Polybenzoxazine (PBZZ) thin films can be fabricated by the plasma‐polymerization technique with, as the energy source, plasmas of argon, oxygen, or hydrogen atoms and ions. When benzoxazine (BZZ) films are polymerized through the use of high‐energy argon atoms, electronegative oxygen atoms, or excited hydrogen atoms, the PBZZ films that form possess different properties and morphologies in their surfaces. High‐energy argon atoms provide a thermodynamic factor to initiate the ring‐opening polymerization of BZZ and result in the polymer surface having a grid‐like structure. The ring‐opening polymerization of the BZZ film that is initiated by cationic species such as oxygen atoms in plasma, is propagated around nodule structures to form the PBZZ. The excited hydrogen atom plasma initiates both polymerization and decomposition reactions simultaneously in the BZZ film and results in the formation of a porous structure on the PBZZ surface. We evaluated the surface energies of the PBZZ films polymerized by the action of these three plasmas by measuring the contact angles of diiodomethane and water droplets. The surface roughness of the films range from 0.5 to 26 nm, depending on the type of carrier gas and the plasma‐polymerization time. By estimating changes in thickness, we found that the PBZZ film synthesized by the oxygen plasma‐polymerization process undergoes the slowest rate of etching in CF₄ plasma. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4063–4074, 2004     

Glucose Monitoring by a Biosensor Based on Mercury Thin Film Electrodes

Abstract

Mercury film electrodes consist of a thin film of mercury deposited on an electrode surface (typically glassy carbon) by reduction of a mercury (II) salt in solution. The surface area/volume ratio is larger for the mercury film electrode, and this electrode is more stable than mercury drop electrode, which allows a faster stirring rate to be used in the deposition step. An enzyme electrode is described, based on glucose oxidase immobilized by gelatin and glutaraldehyde and held over a glassy carbon electrode coated with a thin mercury film. This biosensor responds fast and linearly to glucose in a wide concentration range, which is significant because monitoring of glucose levels is a critical component of diabetes care. Certain optimization and characterization studies were carried out. Average value, standard deviation (SD), and variation coefficient (CV) were calculated with the help of the repeatability studies. Finally, glucose content of human blood samples was monitored with the help of the biosensor presented.     

Crack‐Free Periodic Porous Thin Films Assisted by Plasma Irradiation at Low Temperature and Their Enhanced Gas‐Sensing Performance

Homogenous thin films are preferable for high‐performance gas sensors because of their remarkable reproducibility and long‐term stability. In this work, a low‐temperature fabrication route is presented to prepare crack‐free and homogenous metal oxide periodic porous thin films by oxygen plasma irradiation instead of high temperature annealing by using a sacrificial colloidal template. Rutile SnO₂ is taken as an example to demonstrate the validity of this route. The crack‐free and homogenous porous thin films are successfully synthesized on the substrates in situ with electrodes. The SnO₂ porous thin film obtained by plasma irradiation is rich in surface OH groups and hence superhydrophilic. It exhibits a more homogenous structure and lower resistance than porous films generated by annealing. More importantly, such thin films display higher sensitivity, a lower detection threshold (100 ppb to acetone) and better durability than those that have been directly annealed, resulting in enhanced gas‐sensing performance. The presented method could be applied to synthesize other metal oxide homogenous thin films and to fabricate gas‐sensing devices with high performances.     

Amperometric Glucose Biosensors Based on Composite Polymeric Structures to Prevent Interferences

ABSTRACT

High sensitive glucose biosensors were realised by oxidative polymerisation of amphiphilic pyrrole monomer-glucose oxidase mixtures, previously adsorbed on platinum electrodes. These sensors, based on H₂O₂ electrooxidation at 0.5V vs SCE, exhibited marked interferences due to electrooxidisable endogenous (ascorbate and urate) and exogenous (paracetamol) compounds. Bilayer structures, combining the preceding polymer film as an outer layer and electrogenerated poly(phenylene diamine), overoxidised polypyrrolic films or Nafion as an inner layer, were fabricated in order to minimise interferences. Finally, the use of Nafion as a semipermeable barrier appeared to be more efficient than the electrogenerated films. The Nafion-based biosensor exhibited glucose sensitivity of 0.4 mA.M^?1; .cm^?2, while interference of ascorbate, urate and paracetamol was negligible.     

Sources of instability of ‘wired’ enzyme anodes in serum: urate and transition metal ions

The glucose electrooxidation currents of anodes with films of glucose oxidase and redox polymers electrically connecting (‘wiring’) its redox centers to electrodes decay much more rapidly in serum than in pH 7.2 saline phosphate buffer. Rapid decay is observed also in buffer in the presence of urate and transition metal ions, which are constituents of normal serum. Urate is electrooxidized to dimeric or trimeric products, which precipitate in the electrocatalytic film. Transition metal ions, like Zn²⁺ and Fe²⁺, coordinatively crosslink pyridine or imidazole functions of the redox polymers and also inhibit glucose oxidase.     

Covalent immobilization of glucose oxidase on films prepared by electrochemical copolymerization of 3-methylthiophene and thiophene-3-acetic acid for amperometric sensing of glucose: Effects of polymerization conditions on sensing properties

For the purpose of glucose sensing, enzyme electrodes were fabricated via covalent immobilization of glucose oxidase on the films of conducting polymer. The films were prepared electrochemically by the copolymerization of 3-methylthiophene and thiophene-3-acetic acid. The properties of the films were investigated by taking into account the polymerization conditions (the kind of supporting electrodes, the current, the amount of passed charge, and the monomer concentration) and the dedoping treatment. The glucose sensing performance of the enzyme electrode was found to be affected markedly by the following three factors of the conducting polymer film: surface morphology, conductivity and cohesion with support electrodes. It was suggested that the ideal conducting polymer used for the enzyme electrode should be a thin film having high conductivity and ordered nanostructure.     

Response Characteristics of a Glucose Electrode with a Sensing Membrane Prepared by Plasma Polymerization

A glucose electrode was composed of a dissolved oxygen electrode and an immobilized glucose oxidase membrane prepared by plasma polymerization of propargyl alcohol as a monomer. Fairly good precision of the electrode response to sample solutions was obtained by measurements using the steady-state method or the reaction rate method. Activity of the glucose oxidase immobilized within the membrane and mounted on the electrode lasted for 50 consecutive measurements over 5 days, and, if the membrane was stored in a buffer solution of pH 7.0 at a temperature of 0°C, the activity was preserved for more than 2 months. Such immobilization of the glucose oxidase with the plasma polymer effectively suppressed interference from Cu²⁺ions, which would seriously interrupt oxidation of the glucose in homogeneous solutions, in the sample solutions.     

Amperometric Biosensors for Glucose Based on Layer‐by‐Layer Assembled Functionalized Carbon Nanotube and Poly (Neutral Red) Multilayer Film

Abstract

Multiwalled carbon nanotubes (MWNTs) were treated with a mixture of concentrated sulfuric and nitric acid to introduce carboxylic acid groups to the nanotubes. Conducting polymer film was prepared by electrochemical polymerization of neutral red (NR). By using a layer‐by‐layer method, homogeneous and stable MWNTs and poly (neutral red) (PNR) multilayer films were alternately assembled on glassy carbon (GC) electrodes. With the introduction of PNR, the MWNTs/PNR multilayer film system showed synergy between the MWNTs and PNR, with a significant improvement of redox activity due to the excellent electron‐transfer ability of carbon nanotubes (CNTs) and PNR. The electropolymerization is advantageous, providing both prolonged long‐term stability and improved catalytic activity of the resulting modified electrodes. The MWNTs/PNR multilayer film modified glassy carbon electrode allows low potential detection of hydrogen peroxide with high sensitivity and fast response time. As compared to MWNTs and PNR‐modified GC electrodes, the magnitude of the amperometric response of the MWNTs/PNR composite‐modified GC electrode is more than three‐fold greater than that of the MWNTs modified GC electrode, and nine‐fold greater than that of the PNR‐modified GC electrode. With the immobilization of glucose oxidase onto the electrode surface using glutaric dialdehyde, a biosensor that responds sensitively to glucose has been constructed. In pH 6.98 phosphate buffer, nearly interference‐free determination of glucose has been realized at ?0.2 V vs. SCE with a linear range from 50 µM to 10 mM and response time <10s. The detection limit was 10 µM glucose (S/N=3).     

Polyurethane Enzyme Membranes for Chip Biosensors

Abstract

The coverage of electrochemical chip sensors based on silicon technology with a polyurethane enzyme membrane is described. After crosslinking of the surface by polyfunctional isocyanates the enzyme membrane shows good adhesion, complete retention of the enzyme molecules, and low diffusional resistance to both analytes and products. Using thin film noble metal electrodes and ion sensitive field effect transistors, glucose and urea sensors with good long term stability and short response time have been prepared.     

TiO2 nanotube, nanowire, and rhomboid-shaped particle thin films fixed on a titanium metal plate

Titanium dioxide thin films having various nanostructures could be formed by various treatments on sodium titanate nanotube thin films approximately 5 μm thick fixed on titanium metal plates. Using an aqueous solution with a lower hydrochloric acid concentration (0.01 mol/L) and a higher reaction temperature (90 °C) than those previously employed, we obtained a hydrogen titanate nanotube thin film fixed onto a titanium metal plate by H⁺ ion-exchange treatment of the sodium titanate nanotube thin film. Calcination of hydrogen titanate nanotube thin films yielded porous thin films consisting of anatase nanotubes, anatase nanowires, and anatase nanoparticles grown directly from the titanium metal plate. H⁺ ion-exchange treatment of sodium titanate nanotube thin films at 140 °C resulted in porous thin films consisting of rhomboid-shaped anatase nanoparticles.     

Precise Control of Metal Oxide Thin Films Deposition in Magnetron Sputtering Plasmas for High Performance Sensing Devices Fabrication

Magnetron sputtering deposition is a widely used technique to deposit thin film precisely at nanoscale level. During the deposition of metal oxide thin films, reactive oxygen gas is introduced into the deposition chamber. Pure metal and metal oxide materials can be used as sputter target, although the simplest way is by using a pure metal target. In such reactive process, the effect of target poisoning significantly influence the deposition process and the growth mechanisms of metal oxide thin films became very complex. In general, external parameters such as discharge power, working pressure, reactive gases ratio and substrate temperature are used to optimize the properties of deposited thin films. Then, ex-situ analyses such as scanning electron microscope and X-ray diffraction analysis are performed to obtain the optimized parameter. Sample depositions and ex-situ analyses consume time to achieve the goal through try and error. In this article, in-situ plasma diagnostics are reviewed focusing on an optical emission spectroscopy to precisely control and investigate the sputter target poisoning effect during the deposition of metal oxide thin films. The emission of atomic lines from several metal and oxygen atoms were used to discuss the deposition mechanisms and their correlation with the deposited thin films was observed. Finally, the deposited metal oxide thin films were proposed and tested for several applications such as gas sensor and frequency selective surface glass.     

SnOx Thin Film Gas Sensors Prepared by Plasma Deposition from Tetrabutyltin

Amorphous ultrafine tin-containing organic thin films have been prepared by means of radio frequency (RF) glow-discharge plasma polymerization of tetrabutyltin (TBT). After being annealed, the films turned into ultrafine SnOx thin films, which possessed high gas sensitivity. The influences of the thermal annealing process on the film's composition, microstructure, and gas sensitivity to such reductive gases as EtOH, H ₂ , CH ₄ , and CO were investigated, and the effects of doping silver into the film on its gas sensitivity were also discussed in detail. By doping with Ag, the sensitivity and selectivity of the film obviously increased, the optimum operating temperature decreased, and the film color apparently changed. Based on these facts, the catalysis mechanism of doped Ag is addressed.     

Potentiometric Cholesterol Biosensor Based on ZnO Nanowalls and Stabilized Polymerized Lipid Film

A novel potentiometric cholesterol biosensor was fabricated by immobilization of cholesterol oxidase into stabilized lipid films using zinc oxide (ZnO) nanowalls as measuring electrode. Cholesterol oxidase was incorporated into the lipid film prior polymerization on the surface of ZnO nanowalls resulting in a sensitive, selective, stable and reproducible cholesterol biosensor. The potentiometric response was 57 mV/ decade concentration. The sensor response had no interferences by normal concentrations of ascorbic acid, glucose, and urea, proteins and lipids. The present biosensor could be implanted in the human body because of the biocompatibility of the lipid film.     

Preparation of grain size controlled boron-doped diamond thin films and their applications in selective detection of glucose in basic solutions

Boron-doped diamond (BDD) thin films with different crystal grain sizes were prepared by controlling the reacting gas pressure using hot filament chemical vapor deposition (HFCVD). The morphologies and structures of the prepared diamond thin films were characterized by scanning electron microscopy (SEM) and Raman spectroscopy. The electrochemical responses of K₄Fe(CN)₆ on different BDD electrodes were investigated. The results suggested that electron transfer was faster at the boron-doped nanocrystalline diamond (BDND) thin film electrodes in comparison with that at other BDD thin film electrodes. The prepared BDD thin film electrodes without any modification were used to directly detect glucose in the basic solution. The results showed that the as-prepared BDD thin film electrodes exhibited good selectivity for detecting glucose in the presence of ascorbic acid (AA) and uric acid (UA). The higher sensitivity was observed on the BDND thin film grown on the boron-doped microcrystalline diamond (BDMD) thin film surface, and the linear response range, sensitivity and the low detection limit were 0.25–10 mM, 189.1 μA mmo^?1 cm^?2 and 25 μM (S/N=3) for glucose in the presence of AA and UA, respectively.     

Thermo- and Sulfate-Controllable Bioelectrocatalysis of Glucose Based on Horseradish Peroxidase and Glucose Oxidase Embedded in Poly(N,N-diethylacrylamide) Hydrogel Films

Dual-responsive poly(N,N-diethylacrylamide) (PDEA) hydrogel films with entrapped horseradish peroxidase (HRP) and glucose oxidase (GOD) were successfully prepared on electrode surface with a simple one-step polymerization procedure under mild conditions, designated as PDEA-HRP-GOD. Cyclic voltammetric (CV) response of electroactive probe K₃Fe(CN)₆ at the film electrodes displayed reversible thermo- and sulfate-responsive switching behavior. For example, at 25 °C, the K₃Fe(CN)₆ demonstrated a well-defined CV peak pair with large peak currents for the films, showing the on state, while at 40 °C, the CV response was greatly suppressed and the system was at the off state. The influence of temperature and Na₂SO₄ concentration on the switching behavior of the film system was not independent or separated, but was synergetic. The responsive mechanism of the system was ascribed to the structure change of PDEA component in the films with temperature and sulfate concentration. This switching property of the PDEA-HRP-GOD films could be further used to realize dual-responsive catalytic oxidation of glucose sequentially by HRP and GOD entrapped in the films with Fe(CN)₆ ^3? as the mediator through changing the surrounding temperature and Na₂SO₄ concentration. This system may establish a foundation for fabricating a new type of multi-switchable electrochemical biosensors based on bienzyme electrocatalysis.     

Oxidation of polyethylene surface by glow discharge and subsequent graft copolymerization of acrylic acid

Plasma-induced graft copolymerization of acrylic acid, which was incorporated into PE films, was investigated here. The influence of plasma conditions such as plasma treatment gases, power, pressure, time, monomer concentration, and graft copolymerization time on polymerization yield was determined. The samples were characterized by ESCA, IR, and water contact angle. A respective chemical shift of the C1s signal of Ar or O₂ plasmatreated and untreated PE films was revealed by ESCA, in which the presence of the grafted PAAc was also verified. An increase in polymerization yield with plasma treatment duration and power was found. That the grafted copolymerization was limited to a very thin surface region was revealed by optical microscopy on the cross section of the grafted film. © 1993 John Wiley & Sons, Inc.