Synthesis and characterization of novel thermally stable and optically active poly(amide‐imide)s derived from N,N′‐(4,4′‐diphthaloyl)‐bis‐L‐leucine diacid and aromatic diamines

A new diacid containing optically active functional groups, N,N′‐(4,4′‐diphthaloyl)‐bis‐L ‐leucine diacid ( 3 ), was synthesized and used in a preparation of a series of poly(amide‐imide)s (PAIs) by direct polycondensation with various aromatic diamines in N‐methyl‐2‐pyrrolidinone (NMP). All polymers derived from diacid ( 3 ) were highly organosoluble in the solvents like N‐methyl‐2‐pyrrolidinone, N,N‐dimethylacetamide, N,N‐dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, γ‐butyrolactone, cyclohexanone, and chloroform at room temperature or upon heating. Inherent viscosities of the PAIs were found to range between 0.34 and 0.61·dL g^?1. All the PAIs afforded flexible and tough films. The glass‐transition temperatures of these PAIs were recorded between 212 and 237°C by differential scanning calorimetry, and the 10% weight loss temperatures were ranging from 372 to 393°C and 336–372°C under nitrogen and air, respectively. The polyimide films had a tensile strength in the range of 63–88 MPa and a tensile modulus in the range of 1.2–1.7 GPa. Optically active PAIs exhibited specific rotations in the range of ?10.58° to ?38.70°. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Electrical conduction mechanism in plasma polymerized 2‐(diethylamino)ethyl methacrylate thin films

Thin films of different thicknesses were prepared through glow discharge of 2‐(diethylamino)ethyl methacrylate (DEAEMA) using a capacitively coupled reactor. Current density–voltage (J–V) characteristics for plasma polymerized (PP) DEAEMA thin films of thicknesses 100, 200, 250, and 300 nm in aluminum/PPDEAEMA/aluminum sandwich configuration were studied over the temperature range from 298 to 423 K. J–V curves reveal that in the low‐voltage region, the conduction current obeys Ohm's law while in the high‐voltage region the behavior attributed to be space charge‐limited conduction in PPDEAEMA thin films. The carrier mobility was calculated to be about 6.80 × 10^?19 to 2.38 × 10^?18 m^?2 V^?1s^?1 for various thicknesses. The free carrier density was found to be about 1.78 × 10²³ to 2.04 × 10²³ m^?3, and the trap density was found to be about 6.93 × 10²³ to 15.9 × 10²³ m^?3 for different thicknesses. The activation energies were estimated to be about 0.005–0.016 eV for 2 and 30 V of PPDEAEMA thin films of different thicknesses. The low‐activation energies indicate that the thermally activated hopping conduction is operative in PPDEAEMA thin films. POLYM. ENG. SCI., 55:2729–2734, 2015. © 2015 Society of Plastics Engineers     

Optical characterization of plasma‐polymerized pyrrole‐N,N,3,5‐tetramethylaniline bilayer thin films

A capacitively coupled parallel‐plate reactor has been used to deposit plasma‐polymerized pyrrole (PPPy), plasma‐polymerized N,N,3,5‐tetramethylaniline (PPTMA), and plasma‐polymerized pyrrole‐N,N,3,5‐tetramethylaniline (PPPy‐PPTMA) bilayer thin films on to glass substrates at room temperature. To deposit the bilayer films, pyrrole monomer has been used as the mother material and N,N,3,5‐tetramethylaniline monomer has been deposited in different deposition time ratios after the pyrrole films were formed. Fourier transform infrared (FTIR) and ultraviolet–visible (UV–vis) spectroscopy techniques have been used to characterize the as‐grown thin films of about 500‐nm thick. The structural analyses by FTIR spectroscopy have indicated that the monomer has undergone the reorganization and the ring structure is retained during the plasma polymerization. From the UV–vis absorption spectra, allowed direct transition (E_qd) and allowed indirect transition (E_qi) energy gaps were determined. The E_qd for PPPy, PPTMA, and PPPy‐PPTMA bilayer films are found to be 3.30, 2.85, and 3.65 eV respectively. On the other hand, the E_qi for the same series are 2.25, 1.80, and 2.35 eV, respectively. From these results, it is seen that the energy gaps of the PPPy‐PPTMA bilayer films have been increased compared with the PPPy and PPTMA films. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Dissolution of latex films after γ‐ray treatment

Latex films were prepared by annealing pyrene (Py)‐labeled poly(methyl methacrylate) particles at glass‐transition temperature (100°C). These films were then irradiated by γ‐rays from ⁶⁰Co in a gamma cell at room temperature at the same dose rate (rad/h) for 30 min. Before dissolution films were annealed at elevated temperatures for a 30‐min time interval to complete the film formation process. Steady‐state fluorescence (SSF) technique were used to monitor the dissolution of these irradiated latex films. The dissolution of films in chloroform–heptane (80–20%) mixture was monitored in real time by the Py fluorescence intensity change. Relaxation constants k₀ and desorption coefficients D_d of polymer chains were measured. It was observed that both D_d and k₀ values first increased and then decreased by increasing the annealing temperature. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 129–137, 2002     

Microporous gel electrolyte for quasi‐solid‐state dye‐sensitized solar cell

The extension of electrocatalytic reaction of I^?/I₃^? from counter electrode/gel electrolyte interface to gel electrolyte can significantly enhance the redox kinetics and therefore conversion efficiency of dye‐sensitized solar cells. Microporous gel electrolyte from polypyrrole integrated poly(hydroxyethyl methacrylate/cetytrimethylammonium bromide) [PPy‐integrated poly (HEMA/CTAB)] is successfully synthesized by in‐situ polymerization of pyrrole monomers in three‐dimensional framework of porous poly(HEMA/CTAB) matrix. An ionic conductivity of 12.72 mS cm^?1 and activation energy of 8.65 kJ mol^?1 are obtained from PPy‐integrated poly(HEMA/CTAB) gel electrolyte. Tafel polarization and electrochemical impedance spectroscopy are employed to characterize the electrocatalytic behaviors of the gel electrolytes. The resultant quasi‐solid‐state dye‐sensitized solar cell shows a light‐to‐electrical conversion efficiency of 6.68%. POLYM. ENG. SCI., 54:2531–2535, 2014. © 2013 Society of Plastics Engineers     

Preparation and electrochemical capacitance of poly(pyrrole‐co‐aniline)

The copolymer of pyrrole and aniline, poly(pyrrole‐co‐aniline), has been prepared by chemical oxidation of corresponding monomer mixtures with ammonium peroxysulfate. Techniques of FTIR, SEM‐EDS, and BET surface area measurement were used to characterize the structure and morphology of the copolymer. The electrochemical properties of the copolymer were investigated by cyclic voltammetry, galvanostatic charge‐discharge, and electrochemical impedance spectroscopy. The results indicated that poly(pyrrole‐co‐aniline) was about 100–300 nm in diameter and showed better electrochemical capacitive performance than polypyrrole and polyaniline. The specific capacitance of the copolymer electrode was 827 F/g at a current of 8 mA/cm² in 1 mol/L Na₂SO₄ electrolyte. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Towards enhanced electrochemical capacitance with self‐assembled synthesis of poly(pyrrole‐co‐o‐toluidine) nanoparticles

Poly(pyrrole‐co‐o‐toluidine) (PPOT) nanoparticles for electrochemical capacitors are easily and productively synthesized by a chemical oxidative polymerization of pyrrole (PY) and o‐toluidine (OT) in 0.5M HCl without any external additive. The polymerization yield, electrical conductivity, and size of the copolymer nanoparticles can significantly be optimized by the oxidant/monomer molar ratio and polymerization temperature. The chemical structure of the obtained copolymer is characterized by UV–vis and FTIR. The copolymer nanoparticles synthesized at 10°C are found to generally have irregular granular morphology with a diameter of 60–100 nm and a small polydispersity index of 1.06 by laser particle‐size analyzer, FE‐SEM, and TEM, and good dispersibility in water. The formation mechanism of the nanoparticles is proposed based on the powerful amphipathicity from comonomer aggregate formed by PY and OT in the monomer solution. The PPOT nanoparticles possess a specific capacitance of 310 F g^?1 at 25 mV s^?1 as well as retain 81% of the initial specific capacitance value after 1000 cycles, while its energy density and power density are found to be 40.2 and 1196 W Kg^?1 at 2 A g^?1. The enhanced electrochemical properties can be attributed to the nanostructural advantage of the PPOT. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42995.     

Solid‐state single‐ion conducting comb‐like siloxane copolymer electrolyte with improved conductivity and electrochemical window for lithium batteries

Achievement of high conductivity and electrochemical window at ambient temperature for an all‐solid polymer electrolyte used in lithium ion batteries is a challenge. Here, we report the synthesis and characterization of a novel solid‐state single‐ion electrolytes based on comb‐like siloxane copolymer with pendant lithium 4‐styrenesulfonyl (perfluorobutylsulfonyl) imide and poly(ethylene glycol). The highly delocalized anionic charges of ? SO₂? N^(–)? C₄F₉ have a weak association with lithium ions, resulting in the increase of mobile lithium ions number. The designed polymer electrolytes possess ultra‐low glass transition temperature in the range from ?73 to ?54 °C due to the special flexible polysiloxane. Promising electrochemical properties have been obtained, including a remarkably high conductivity of 3.7 × 10^?5 S/cm and electrochemical window of 5.2 V (vs. Li⁺/Li) at room temperature. A high lithium ion transference number of 0.80, and good compatibility with anode were also observed. These prominent characteristics endow the polymer electrolyte a potential for the application in high safety lithium ion batteries. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45848.     

Synthesis and properties of poly(amide–imide)s based on N,N′‐bis(4‐carboxyphenyl)‐4,4′‐oxydiphthalimide,p‐aminobenzoic acid and various aromatic diamines

A new diimide–diacid monomer, N,N′‐bis(4‐carboxyphenyl)‐4,4′‐oxydiphthalimide (I), was prepared by azeotropic condensation of 4,4′‐oxydiphthalic anhydride (ODPA) and p‐aminobenzoic acid (p‐ABA) at a 1:2 molar ratio in a polar solvent mixed with toluene. A series of poly(amide–imide)s (PAI, III_a–m) was synthesized from the diimide–diacid I (or I′, diacid chloride of I) and various aromatic diamines by direct polycondensation (or low temperature polycondensation) using triphenyl phosphite and pyridine as condensing agents. It was found that only III_k–m having a meta‐structure at two terminals of the diamine could afford good quality, creasable films by solution‐casting; other PAIs III using diamine with para‐linkage at terminals were insoluble and crystalline; though III_g–i contained the soluble group of the diamine moieties, their solvent‐cast films were brittle. In order to improve their to solubility and film quality, copoly(amide–imide)s (Co‐PAIs) based on I and mixtures of p‐ABA and aromatic diamines were synthesized. When on equimolar of p‐ABA (m = 1) was mixed, most of Co‐PAIs IV had improved solubility and high inherent viscosities in the range 0.9–1.5 dl g^?1; however, their films were still brittle. With m = 3, series V was obtained, and all members exhibited high toughness. The solubility, film‐forming ability, crystallinity, and thermal properties of the resultant poly(amide–imide)s were investigated. © 2002 Society of Chemical Industry     

Impedance spectroscopy of N‐substituted oligo‐oxyethylene polypyrrole films

The electrochemical properties of neutral (dedoped) and oxidized (doped) poly(1,11‐bis(1,1‐pyrrole)‐3,6,9‐trioxaundecane) (poly‐ I ) film electrodes were investigated using cyclic voltammetry and electrochemical impedance spectroscopy (EIS) techniques. Poly‐ I was deposited on glassy carbon electrode (GCE) from acetonitrile solution containing 5.0 × 10^?3M 1,11‐bis(1,1‐pyrrole)‐3,6,9‐trioxaundecane ( I ) and 0.1M LiClO₄ supporting electrolyte. Doped poly‐ I exhibits a single semicircle in its complex‐capacitance plots, indicating a single dominant ion transport process, together with high capacitance values. These features make this polymer film a candidate for an energy storage material. Also, poly‐ I can be a candidate as a sensory material for the detection of Ag⁺ based on impedance parameters. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Solid polymer electrolytes. XI. Preparation,characterization and ionic conductivity of new plasticized polymer electrolytes based on chemical‐covalent polyether–siloxane hybrids

A new hybrid polymer electrolyte system based on chemical‐covalent polyether and siloxane phases is designed and prepared via the sol–gel approach and epoxide crosslinking. FT‐IR, ¹³C solid‐state NMR, and thermal analysis (differential scanning calorimetry (DSC) and TGA) are used to characterize the structure of these hybrids. These hybrid films are immersed into the liquid electrolyte (1M LiClO₄/propylene carbonate) to form plasticized polymer electrolytes. The effects of hybrid composition, liquid electrolyte content, and temperature on the ionic conductivity of hybrid electrolytes are investigated and discussed. DSC traces demonstrate the presence of two second‐order transitions for all the samples and show a significant change in the thermal events with the amount of absorbed LiClO₄/PC content. TGA results indicate these hybrid networks with excellent thermal stability. The EDS‐0.5 sample with a 75 wt % liquid electrolyte exhibits the ionic conductivity of 5.3 × 10^?3 S cm^?1 at 95°C and 1.4 × 10^?3 S cm^?1 at 15°C, in which the film shows homogenous and good mechanical strength as well as good chemical stability. In the plot of ionic conductivity and composition for these hybrids containing 45 wt % liquid electrolyte, the conductivity shows a maximum value corresponding to the sample with the weight ratio of GPTMS/PEGDE of 0.1. These obtained results are correlated and used to interpret the ion conduction behavior within the hybrid networks. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1000–1007, 2006     

Preparation of conducting polyacrylonitrile/polypyrrole composite films by electrochemical synthesis and their electrical properties

Electrically conducting polyacrylonitrile (PAN)/polypyrrole (PPy) composite films were prepared by electrochemical polymerization of pyrrole in an insulating PAN matrix under various polymerization conditions and their electrical properties were studied. The conductivities of PAN/PPy composite films peeled off from the platinum electrode he lie in the range of 10^?2–10^?3 s/cm, depending on the preparation conditions: The conductivity increased with the concentrations of the electrolyte and the monomer, but it decreased with the polymerization temperature of pyrrole and the applied potential.     

Melt fracture behavior of polypropylene‐type resins with narrow molecular weight distribution. I. Temperature dependence

Polypropylene (PP)‐type resins with narrow molecular weight distribution, such as PP‐type thermoplastic elastomer PER and controlled‐rheology PP (CRPP) made by peroxide degradation of high molecular weight PP, have a problem of easy generation of skin roughness at extrusion. To examine the present state, the occurrence of skin roughness in PER and CRPP at extrusion was investigated with a capillary rheometer in a shear rate range of 12–6100 s^?1 and a temperature range of 180–280°C. A homo‐PP (HPP) and a block‐PP (BPP) with usual molecular weight distributions were used for comparison. HPP and BPP with usual molecular weight distributions show smooth extrudates at low shear rates and abruptly generate severe skin roughness “elastic failure” originating at the die entrance at a higher shear rate. PER and CRPP with narrow molecular weight distributions easily generate “sharkskin” melt fracture originating at the die exit, from a shear rate nearly one decade lower than rates of elastic failure of HPP and BPP. The sharkskin becomes more severe, with increasing shear rate, and attains to the elastic failure. The critical shear rate at which sharkskin occurs increases with increasing extrusion temperature. The critical shear rate is about 20 s^?1 at 180°C and about 120 s^?1 at 280°C, which is in the range encountered by the molten resin at extrusion processing. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2111–2119, 2002     

Synthesis of novel polyurethanes containing dioxybenzylidenecyanoacetate,as non‐linear optical chromophores and their properties

Methyl 3,4‐di‐(2′‐hydroxyethoxy)benzylidenecyanoacetate (3) was prepared by hydrolysis of methyl 3,4‐di‐(2′‐vinyloxyethoxy)benzylidenecyanoacetate (2). Diol 3 was condensed with 2,4‐toluenediisocyanate, 3,3′‐dimethoxy‐4,4′‐biphenylenediisocyanate, and 1,6‐hexamethylenediisocyanate to yield polyurethanes 4, 5 and 6 containing the non‐linear optical (NLO) chromophore 3,4‐dioxybenzylidenecyanoacetate. The resulting polyurethanes 4–6 were soluble in common organic solvents such as acetone and DMF. T_g values of the polymers obtained from DSC thermograms were in the range 80–102 °C. Polymers 4–6 showed thermal stability up to 300 °C in TGA thermograms, and electro‐optic coefficients (r₃₃) of the poled polymer films were in the range 10–12 pm V^?1 at 633 nm, which are acceptable for NLO device applications. © 2002 Society of Chemical Industry     

Dewetting and microphase separation in symmetric polystyrene‐block‐polyisoprene diblock copolymer ultrathin films

The kinetics of surface structure evolution in ultrathin films of low‐molecular‐weight polystyrene‐block‐polyisoprene (M_w: 7300 g mol^?1–7300 g mol^?1) diblock copolymer at temperatures below the bulk order‐to‐disorder transition temperature are presented. Films with two different thicknesses were studied as a function of annealing temperature using atomic force microscopy. These film thicknesses enabled the investigation of the competition between microphase separation and dewetting that resulted in two different morphologies: long‐range bicontinuous structures and random holes. Three distinctive stages of structure evolution were observed in bicontinuous structure, with the underlying mechanism compared with spinodal dewetting. Thicker films presented holes on their surfaces upon annealing at elevated temperatures, and kinetics of formation of the holes were discussed. We found that the molecular mobility determined the rates of dewetting, while the microphase separation hardly affected the dewetting process. © 2015 Society of Chemical Industry     

Synthesis and characterization of organo‐soluble fluorinated polyimides

A novel fluorinated diamine monomer with a keto group, 4‐[4‐amino‐2‐trifluoromethyl phenoxy]‐4′‐[4‐aminophenoxy]benzophenone (ATAB) was prepared by reacting dihydroxybenzophenone with 4‐chloronitrobenzene and 2‐chloro‐5‐nitrotrifluoromethylbenzene in the presence of potassium carbonate followed by catalytic reduction with palladized carbon (10%). Fluorinated polyimides IVa–e were synthesized from the diamine mentioned above via a two‐step method (thermal and chemical imidization). Polyimides IVa–e have inherent viscosities in the range 0.65–1.06 dL g^?1 (thermal imidization) and 0.82–1.56 dL g^?1 (chemical imidization). The polyimides prepared by chemical imidization exhibit excellent solubility. Polyimide films exhibit tensile strength, elongation and tensile modulus in the ranges 96–106 MPa, 9–13% and 1.1–1.7 GPa, respectively. The T₁₀ values of the polyimides are in the range 540–598 °C in nitrogen and 545–586 °C in air, with more than 50–60% char yield. They have T_g values between 244 and 285 °C. The prepared polyimides show cut‐off wavelengths in the range 365–412 nm and transmittance at 450 nm in the range 80.9–94.2%. The dielectric constants of the polyimide films are in the range 3.10–3.77 at 1 kHz and 3.04–3.66 at 10 kHz, with moisture absorption of 0.14–0.40%. Copyright © 2006 Society of Chemical Industry     

Ionic conductivity and morphology of semi‐interpenetrating‐type polymer electrolyte entrapping poly(siloxane‐g‐allyl cyanide)

We prepared a semi‐IPN (interpenetrating network)‐type solid polymer electrolyte (SPE) using poly (ethylene glycol)dimethacrylate (PEGDMA) as a polymer matrix containing a monocomb‐type poly(siloxane‐g‐allyl cyanide) and poly(ethylene glycol)dimethylether (PEGDME) for the lithium secondary battery. The poly(siloxane‐g‐allyl cyanide)s were prepared by a hydrosilation reaction of poly (methyl hydrosiloxane) with allyl cyanide and characterized by ¹H NMR and FTIR. The semi‐IPN‐type electrolyte was prepared by thermal curing, and conductivities of samples were measured by impedance spectroscopy using an indium tin oxide (ITO) electrode. The ionic conductivity of the semi‐IPN‐polymer electrolyte was about 1.05 × 10^?5 S cm^?1 with 60 wt % of the poly(siloxane‐g‐allyl cyanide) and 6.96 × 10^?4 S cm^?1 with 50 wt % of the PEGDME and 10 wt % of the poly(siloxane‐g‐allyl cyanide) at 30°C. The SEM morphology of the cross section of the semi‐IPN‐polymer electrolyte film was changed from discontinuous network to continuous network as increasing the PEGDME content and decreasing the poly(siloxane‐g‐allyl cyanide) content. The mechanical stability was also enhanced when increasing the PEGDME content. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

New organic semiconductor materials: electrical conductivity,thermal properties and application of voltage‐controlled negative resistance device of poly[(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid)‐co‐(maleic acid)]

BACKGROUND: Electrical conductivity, photoconductivity, voltage‐controlled negative resistance and thermal properties of copolymers of 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid and maleic acid were investigated in order to obtain new organic semiconductors. RESULTS: The room temperature conductivity of three different copolymers was found to be in the range 1.28 × 10^?8 ? 1.20 × 10^?7 S cm^?1. The dark‐ and photo‐current‐voltage characteristics indicate that the copolymers exhibit voltage‐controlled differential negative resistance behaviour. The electrical conductivity of the polymers increases by photo‐illumination, suggesting that the polymers exhibit photoconductivity. The width of the exponential tail in the forbidden band gap of the three polymers was determined via the transient photocurrent technique and E₀ values were in the range 34.4–36.49 meV. CONCLUSION: The results suggest that the copolymers could be used as organic semiconductor materials. Copyright © 2007 Society of Chemical Industry     

Graft copolymerization of acrylic acid on methylcellulose by ceric ion/p‐xylene redox pair

The graft copolymerization of acrylic acid onto methylcellulose by ceric ion/p‐xylene redox pair was investigated in aqueous media under homogeneous conditions. The graft yield dependency on p‐xylene concentration in the range 1.8–45.0 × 10^?5M showed a minimum and an enhanced yield when the methylcellulose interacted with ceric ion and p‐xylene for an initial period of 10 min (preoxidation time) prior to addition of monomer to the reaction medium. This was attributed to the presence of two kinetically controlled reactions initiated by p‐xylyl radical and diradical species. At prolonged preoxidation times of 30 and 60 min, the graft yield dependency on p‐xylene concentration was normal and suggested the presence of only one initiating species. The effect of ceric ion on the graft reaction in the concentration range of 8.33–83.3 × 10^?3M was optimal at 131% graft yield for ceric ion concentration of 16.7 × 10^?3M and was reduced significantly by as much as 75% at the highest concentration of the latter. The temperature dependency of graft yield was negative in the region 30–50°C. At 50°C the initial rate of graft was only 37% of the value at 30°C. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 500–504, 2002; DOI 10.1002/app.10200     

Poly(hydroxyethyl methacrylate‐co‐glycidyl methacrylate) reactive membrane utilised for cholesterol oxidase immobilisation

Poly(2‐hydroxyethyl methacrylate‐co‐glycidyl methacrylate) p(HEMA–GMA) membrane was prepared by UV‐initiated photopolymerisation of 2‐hydroxyethyl methacrylate (HEMA) and glycidyl methacrylate (GMA) in the presence of an initiator, azobisisobutyronitrile (AIBN). Cholesterol oxidase was immobilised directly on the membrane by forming covalent bonds between its amino groups and the epoxide groups of the membrane. An average of 53 µg of enzyme was immobilised per cm² of membrane, and the bound enzyme retained about 67% of its initial activity. Immobilisation improved the pH stability of the enzyme as well as its temperature stability. The optimum temperature was 5 °C higher than that of the free enzyme and was significantly broader. The thermal inactivation rate constants for free and immobilised preparations at 70 °C were calculated as k_{i (free)} 1.06 × 10^?1 min^?1 and k_{i (imm)} 2.68 × 10^?2 min^?1, respectively. The immobilised enzyme activity was found to be quite stable in the repeated experiments. © 2002 Society of Chemical Industry