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     

A comparison of properties of inulinases of Fusarium oxysporum immobilised on various supports

Extracellular inulinase was obtained after growing Fusarium oxysporum for 9 days on a medium containing an aqueous extract of Cichorium intybus roots. After partial purification, inulinase was immobilised by cross-linking it with water insoluble protein supports prepared from flour of soybean and mungbean, and egg white. Inulinase was also immobilised by adsorbing it on DEAE-cellulose. Inulinase immobilised on soybean and mungbean supports had a higher optimum temperature of 45°C as compared to 37°C of the free enzymes. Inulinase adsorbed on DEAE-cellulose was thermally the most stable whereas the inulinase cross-linked on soybean support was the least stable. Inulinase immobilised on DEAE-cellulose and on supports obtained from mungbean and soybean had a pH optima of 5.5, 6.5 and 6.0, respectively. The K_m values of various immobilised inulinases with inulin varied from 0.25 to 0.44 mmol dm^?3.     

Steady state behaviour of three phase air lift bioreactors – an integrated model and experimental verification

Beneckea natriegens growing both in suspension and immobilised on diatomaceous earth (silica) support particles, in a 3 dm three phase air lift bioreactor (TPALB), was employed to demonstrate the relationship between substrate loading rate and immobilised biomass loading at steady state. Sterile conditions were maintained during the experiments, while the hydraulic conditions and the inlet flowrate remained constant. The experiment ran for 12 days, whilst the inlet substrate (n‐propanol) concentration was varied both upwards and downwards between 250 and 750 mg dm⁻³. The bulk liquid substrate concentration and the immobilised biomass loading were found to vary between 6–120 mg dm⁻³ and 71–159 mg(dry biomass) g⁻¹ (silica), respectively. The experimental results demonstrated that there is a positive relationship between substrate loading and immobilised biomass loading. A mathematical model is proposed to calculate biofilm thickness and bulk liquid substrate concentration (for steady state) using the inlet flowrate and the inlet substrate concentration as input parameters. The model was able to predict both biofilm thickness and immobilised biomass loading for the lower substrate loading rates applied. © 1999 Society of Chemical Industry     

Biosorption of heavy metals from aqueous solution using modified activated carbon: comparison of linear and nonlinear methods

BACKGROUND: Biosorption of heavy metals from aqueous solution by modified activated carbon with Phanerochaete chrysosporium immobilised in Ca‐alginate beads was investigated using a batch system and comparison of linear and nonlinear methods. RESULTS: The amount of Cu(II), Zn(II) and Pb(II) ion sorption by the beads was as follows: activated carbon with P. chrysosporium immobilised in Ca‐alginate beads (ACFCA) (193.4, 181.8, 136.6 mg g^?1) > activated carbon immobilised in Ca‐alginate beads (ACCA) (174.8, 162.0, 130.7 mg g^?1) > P. chrysosporium (F) (148.8, 125.6, 120.4 mg g^?1) > activated carbon (AC) (138.8, 112.3, 109.3 mg g^?1) > plain Ca‐alginate beads (PCA) (125.4, 105.2, 98.2 mg g^?1). The widely used Langmuir and Freundlich isotherm models were utilised to describe the biosorption equilibrium process. CONCLUSION: The results of this study suggest that the immobilisation of modified activated carbon with P. chrysosporium in Ca‐alginate beads is suitable for a batch system. The isotherm parameters were estimated using linear and nonlinear regression analyses. The surface charge density of the biosorbents varied with the pH of the medium; the maximum biosorption of heavy metal ions on the biosorbents was obtained when the pH was between 5.6 and 7.4. Copyright © 2008 Society of Chemical Industry     

Immobilised plant cells: General aspects

The immobilisation of plant cells grown in suspension cultures by entrapment in various gels is described. The viability and biosynthetic capacity of such immobilised cells have been investigated. Model studies covering different aspects of biosynthesis, i.e. biotransformation, synthesis from added precursors and synthesis de novo from a simple carbon source, are described. In some model studies it has been observed that the immobilised cells can produce higher amounts of secondary products than freely suspended cells under the same conditions. Furthermore the permeabilisation of plant cells for continuous release of formed products with subsequent immobilisation is also discussed.     

Removal of direct Red‐31 and direct Orange‐26 by low cost rice husk: Influence of immobilisation and pretreatments

The aim of the present study is to investigate the influence of free, carboxymethyl cellulose (CMC) immobilised, PVA–alginate immobilised, and HCl treated rice husk on the removal of Direct Red‐31 and Direct Orange‐26 dyes. The biosorption capacity of the rice husk increased with HCl treatment (67.39 and 45.34 mg/g) and decreased with PVA–alginate immobilisation (9.73 and 10.03 mg/g) as compared to the free biomass (65.56 and 45.58 mg/g) at 200 mg/L dye concentration for Direct Red‐31 and Direct Orange‐26, respectively. Equilibrium data were best described by Langmuir Type 1 for Direct Red‐31 and Direct Orange‐26 (free, CMC immobilised, PVA–alginate immobilised, and HCl treated). Best correlation coefficients for Direct Red‐31 and Direct Orange‐26 using free, CMC immobilised, PVA–alginate immobilised, and HCl treated rice husk were obtained for pseudo‐second order and Elovich kinetic models. Values of Gibbs free energy (ΔG°) and enthalpy change (ΔH°) indicated that reaction was spontaneous and endothermic in nature at the studied temperatures. FT‐IR studies showed the involvement of carbonyl, carboxyl, and amide groups in the biosorption process. SEM exhibited the morphological changes on the biosorbent surface and BET analysis to determine the surface area is also carried out.     

Effect of Immobilisation on the Production of α-Amylase by an Industrial Strain of Bacillus amyloliquefaciens

The effect of immobilisation of an industrial strain of Bacillus amyloliquefaciens in calcium alginate beads on production of α-amylase was investigated using lactose-based media in shake flasks and in a 0.3 dm³ glass fermenter. Although the microorganism was a good α-amylase producer in batch cultures of free cells, it was unable to produce the enzyme for extended periods either in repeated batch cultures, or in continuous cultivation. In each case, parallel tests with cells immobilised in calcium alginate beads gave still further reduced enzyme yields, and the free cells released into the broth from these beads probably contributed substantially to any amylase produced during these extended fermentations. After prolonged use, the core of the alginate beads accumulated hard insoluble material, with viable immobilised cells confined to a surface layer.     

In vivo evaluation of the effects of continuous exercise on skeletal muscle triglycerides in trained humans

Magnetic resonance spectroscopy (¹H MRS) and imaging (MRI) were used to investigate the effects of a bout of moderate prolonged exercise on intra (IMCL)- and extramyocellular lipid (EMCL) utilization in the soleus, tibialis anterior, and gastrocnemius muscles of five trained human subjects. MRI and ¹H MRS measurements were obtained before and after a 90 min run on a calibrated treadmill at a velocity corresponding to 64±1.5% of each subjects' maximal rate of oxygen consumption. There were significant decreases in IMCL following exercise in the tibialis (pre: 22.37±4.33 vs. post: 15.16±3.25 mmol/kg dry wt; P<0.01) and soleus (pre: 36.93±1.45 vs. post: 29.85 ±2.44 mmol/kg dry wt; P<0.01) muscles. There was also a decrease in the gastrocnemius muscle, although this did not reach the level of significance (pre: 33.78±5.35 vs. post: 28.48±5.44 mmol/kg dry weight; P<0.10). No significant changes were observed in EMCL or subcutaneous fat. In conclusion, this study showed that IMCL were significantly utilized in the tibialis and soleus muscles of aerobically endurance-trained humans. The absence of significant utilization of IMCL in the gastrocnemius may reflect differences in fiber type and/or intensity of contraction for each muscle group.     

Continuous alcohol production from whey permeate using immobilised cell reactor systems

The present paper reports the performance of a bioreactor packed with alginate-entrapped Kluyveromyces marxianus NCYC179 for continuous fermentation of whey permeate to ethanol. A maximum ethanol productivity as 28.21 gl^?1 h^?1 was attained at D=0.42h^?1 and 75% lactose consumption (substrate feed rate in the inflowing medium was 200 g lactose I^?1). However, the higher dilution rates (0.6-1.Oh^?1) resulted in poor productivities and higher substrate washout in the effluent samples. The maximum specific ethanol production (qpi) and maximum specific lactose uptake (qsi) of the immobilised Kluyveromyces marxianus NCYC179 was found to be 3.88g ethanol/g immobilised cell/hx10^?2 and 8.75g lactose consumed/g immobilised cell/hx10^?2 respectively. A bead size of 2.5 mm in diameter and activation period of 24h of alginate beads in lactose solution (10%) prior to their packing in column reactor were found to support the efficient working of the bioreactor. The immobilised cell bioreactor system was operated continuously at a constant dilution rate of 0.15h^?1 and 10% lactose for 562 h without any significant change in the efficiency (varied from 84 to 88% of theoretical) and viability of the entrapped yeast cells (dropped from 84 to 81%).     

Factors affecting silver biosorption by an industrial strain of Saccharomyces cerevisiae

Factors affecting silver biosorption by Saccharomyces cerevisiae biomass, obtained as a waste product from industry, were examined. Maximum removal of silver from solution was achieved within 5 min. Increasing the concentration of biomass in experimental flasks from 1 to 8 mg cm⁻³ decreased both silver accumulation, from 224·7 to 89·5 μmol Ag g⁻¹ dry wt, and associated H⁺ ion release, from 109·4 to 31·7 μmol H⁺ g⁻¹ dry wt. The presence of 1·0 mol dm⁻³ cadmium or methionine decreased silver biosorption by 40% and 93% respectively. Boiling in 100 mmol dm⁻³ NaOH or 10 mmol dm⁻³ sodium dodecyl sulphate decreased silver biosorption by 54% and 25% respectively. A temperature increase from 4°C to 55°C decreased silver biosorption by 9%. The metabolic state of the yeast had no effect on silver biosorption. Decreasing the pH of the silver solution caused a reduction in metal removal by the biomass.     

Continuous fixed bed biosorption of Cu2+ ions: application of a simple two parameter mathematical model

Biomass from two fungi of the Mucorales order, laboratory cultured and immobilised Rhizopus arrhizus, and industrial waste Mucor miehei, was tested for capacity to adsorb copper from solution in batch and continuous‐flow column systems. Maximum uptake levels were c 400 and 300 mmol g⁻¹ (dry weight) respectively. Immobilisation of Rhizopus arrhizus in polyvinyl formal to cell loadings of 60% (w/w) did not diminish metal uptake levels. In continuous‐flow columns both biosorbents adsorbed copper to levels equal or approaching the batch uptake values. Column breakthrough curves were fitted to a two parameter model and each of the parameters, σ and t₀ , were linearly correlated with column operating parameters. Predicted breakthrough curves agreed closely with experimental values. © 1999 Society of Chemical Industry     

The preparation of an immobilised glucose isomerase II. Immobilisation and properties of the immobilised enzyme

Glucose isomerase ex Lactobacillus brevis was successfully immobilised on microcrystalline cellulose, using the transition metal-link method. Immobilisation could be performed over a pH range of 5 to 9, and usually resulted in an apparent specific activity increase. The immobilised glucose isomerase generally displayed properties similar to those of the soluble enzyme, with the exception of the following differences:

• (i) a pH optimum at pH = 6, an acid shift of 0.5 units on immobilisation;
• (ii) an optimum reaction temperature at 50 °C, lower than that for the soluble enzyme;
• (iii) on incubation at 4 °C, a retention of 53% of the initial specific activity, when stored in 0.02 M, pH = 7, Tris buffer, after 8 weeks, compared with an apparent activation of the soluble enzyme after 10 and 19 weeks' storage.

Storage properties of the immobilised enzyme at 4 °C in Tris were apparently improved by the presence of Mn⁺⁺ and Co⁺⁺, although associated with some protein release. Storage at 4 °C in water alone, as opposed to Tris, resulted in a more rapid activity loss.     

Study of a newly isolated thermophilic bacterium capable of Kuhemond heavy crude oil and dibenzothiophene biodesulfurization following 4S pathway at 60 °C

BACKGROUND: To meet stringent emission standards stipulated by regulatory agencies, the oil industry is required to bring down the sulfur content in fuels. As some compounds cannot be desulfurized by existing desulfurizing processes (such as hydrodesulfurization, HDS) biodesulfurization has become an interesting topic for researchers. Most of the isolated biodesulfurizing microorganisms are capable of desulfurization of refined products whose predominant sulfur species are dibenzothiophenes so biocatalyst development is still needed to desulfurize the spectrum of sulfur‐bearing compounds present in whole crude. RESULTS: The first desulfurizing bacterium active at 60 °C has been isolated, which reduces DBT concentration from 2 mmol L^?1 to 0.1 mmol L^?1 after 95 h, following the 4S pathway. Its DBT desulfurization pattern was represented by the Michaelis‐Menten equation. Various parameters such as V_max, K_m, µ_m, K_s and maximum specific DBT desulfurization rate were calculated which are 0.092 mmol L^?1 h^?1, 3.554 mmol L^?1, 0.157 h^?1, 3.722 mmol L^?1 and 0.192 mmol L^?1 DBT g^?1 DCW (dry cell weight) h^?1, respectively. It can desulfurize 50% of the sulfur content of Kuhemond heavy crude oil (KHC oil) with an initial sulfur content of 7.6%wt in 6 days. Its maximum specific desulfurization rate for KHC oil is equivalent to 0.005 g sulfur g^?1 DCW h^?1. The bacterium was isolated during a heavy crude oil biodesulfurization project initiated by PEDEC, a subsidiary of National Iranian Oil Company. CONCLUSION: The KHC oil sulfur removal efficiency of the bacterium is approximately five times that of BBRC‐9016 bacterium. It removes sulfur selectively without using sulfur‐containing compounds as its carbon source. By applying various media during its isolation, the probability of screening the correct microorganism is increased. Copyright © 2008 Society of Chemical Industry     

In situ reactive extraction of lactic acid from fermentation media

Extractive lactic acid fermentation was investigated in the presence of sunflower oil and Alamine‐336 (with oleyl alcohol as the diluent solvent). Lactic acid was produced in various media at 37 °C using Lactobacillus delbrueckii (NRRL‐B 445). First, the effects of oleyl alcohol (33.3%, v/v), immobilisation, and immobilisation in the presence of sunflower oil (5, 10, 15%, v/v) on lactic acid production were investigated. It was found that oleyl alcohol did not affect production while addition of sunflower oil increased lactic acid production from 10.22 to 16.46 gdm^?3. On the other hand, a toxic effect was observed for oleyl alcohol solutions containing 15–50% (v/v) Alamine‐336. A maximum total lactic acid concentration of 25.59 gdm^?3 was obtained when an oleyl alcohol solution containing 15% (v/v) Alamine together with immobilised cells with 15% (v/v) sunflower oil was used. This value was about 2.5 times that obtained from fermentation without organic solutions. © 2001 Society of Chemical Industry     

Allelopathic potential in bilberry-spruce forests: Influence of phenolic compounds on spruce seedlings

Regeneration failure ofPicea abies in a subalpine bilberry-spruce forest was studied in relation to phenolic compounds, their occurrence and toxicity. Germination bioassays with natural leachates of bilberry (Vaccinium myrtillus) and spruce showed negative effects on root elongation of spruce seedlings. Growth bioassays on litter and humus demonstrated inhibitory effects of these organic layers.p-Hydroxyacetophenone, a spruce-specific metabolite, was isolated in spruce throughfall (10^–6 M), in water extracts of litter (between 1 and 8 µg/g dry wt) and organic layer (less than 1 µg/g dry wt) in addition to tannins and several common phenolic acids. Potential relationships between vegetation cover and phenolic pattern of the soil are discussed, since organic layers under bilberry heath exhibited higher amounts of phenolic acids and tannins than those under spruce.p-Hydroxyacetophenone and caffeic acid reduced, even at 5 × 10^–5 M, spruce seedling growth, especially root development, with additive effects for these two monomers. Autotoxicity involving spruce trees and allelopathy of understory species, mediated byp-hydroxy-acetophenone and other phenolic compounds, including tannins, deserves further attention in regeneration studies.     

Studies on the structural features of sodium alginate entrapped Kluyveromyces marxianus NCYC179 cells used for alcohol production from whey permeate

Alginate-entrapped living Kluyveromyces marxianus NCYC179 cells were successfully used in alcohol production from whey permeate. Using 10% whey lactose as substrate, an alcohol production efficiency of 81.5–84.9% and 84.0–88.2% with cell viability maintenance between 82.8–84.3% and 81.0–84.3% of the immobilised cells during the monitoring periods, in batch (six repeat runs) and continuous (23 days of experimenting time) systems, respectively. The immobilised samples remained stable during the course of fermentation with no leakage of K. marxianus cells into the surrounding medium in the case of the batch system. However, slight leakage after 10 days of continuous run in the continuous process was recorded. The scanning electron microscopic studies of the beads containing entrapped yeast cells and sections or crushed samples of the beads carried out at the start and termination of fermentation in both the processes (batch and continuous) revealed that the immobilisation procedure does not influence any morphological change in the entrapped cells during the prolonged periods of fermentation. Moreover, the gel matrix structure was also found to be unaffected by the fermentation conditions employed during the course of present studies.     

Production of Hexanoic Acid by Free and Immobilised Cells of Megasphaera elsdenii: Influence of in-situ Product Removal Using Ion Exchange Resin

The objective of this work was to improve the production of hexanoic acid by the anaerobic rumen bacterium, Megasphaera elsdenii, using product removal and immobilised cell approaches. Hexanoic acid, the major product of glucose metabolism by M. elsdenii strain ATCC25940, was produced at concentrations of 2–3 g dm⁻³ in stirred batch cultures. With pH controlled manually at 7, maximum concentrations of hexanoic acid increased to 6–8 g dm⁻³ with yields (g product per g glucose used) of approximately 30%. When an anion exchange resin, Amberlite IRA 400, was added during early stages of culture to minimise product inhibition, growth was not impaired and cell lysis, which was commonly seen during the stationary phase in control fermentations, was prevented. The presence of resin in pH-controlled, stirred batch fermentations increased the rate of glucose consumption and doubled hexanoic acid productivity: the equivalent of 11 g dm⁻³ of hexanoic acid was made with an estimated yield of up to 39%. Cells were immobilised successfully in κ-carrageenan and, when cell densities in inocula were sufficiently high, rates of glucose consumption and product formation were similar to free cells. Including resin in cultures of immobilised cells had effects similar to those above. Using a fed-batch mode with immobilised cells cultured in the presence of resin further increased final concentrations of hexanoic acid (up to 19 g dm⁻³) but yields were lower (20–30%) and productivity did not increase. These results show that production of volatile fatty acids can be improved significantly by product stripping onto an anion exchange resin. © 1997 SCI.     

Effect of Carrier Matrix on Fermentative Production of Ethanol by Surface Immobilised Yeast Cells

The production of ethanol for potable preparations is well established and the traditional methods used therein are changing. More important, however, has been the advent of fuel alcohol, first in Brazil, but now with ever-increasing possibilities of being adopted in North America and Europe. Production of alcohol by fermentation has therefore come to stay, and it is essential to discover ways of improving the productivities of such fermentations. The effect of organic (cellulose and corn stover) and inorganic matrices (silica gel, porous silica, Celite and derivatised Celite) on the performance of ethanol fermentation by Saccharomyces bayanus was tested. The hydrophilicity degree of the support seems to play an important role in the ability of reaching high ethanol concentrations in the fermentation of 300 g dm^?3 of glucose. Cells immobilised on carriers with low hydrophilicity degree, namely Celite, lead to better results (residual glucose: 56 g dm^?3; ethanol: 111 g dm^?3) than their free counterparts (residual glucose: 136 g dm^?3; ethanol: 71 g dm^?3). Celite was selected for further cell immobilisation studies, including time of adsorption, whole cell concentration, initial glucose concentration and time of addition of the support to the fermentation medium. The latter has revealed to be a very important factor, improving the performance of ethanol fermentation by reducing the fermentation time. Previous immobilisation seems to have no effect when compared with the simple addition of Celite to the inoculated medium and the eficiency of Celite did not increase when the concentration of glucose was enhanced.     

Molten salt synthesis of nitrogen-doped porous carbons for hydrogen sulfide adsorptive removal

Nitrogen-doped porous carbons (NPCs) with high hydrogen sulfide (H₂S) adsorption capacity have been prepared through the molten-salt approach, using d-glucose as carbon source, melamine as nitrogen source and eutectic salt (LiCl/KCl) as porogen. The NPCs possess tunable nitrogen content (3.07–24.31 wt.%) and specific surface area (451–1190 m²/g) with the changing of the weight ratio of nitrogen source to carbon source and synthesis temperature. The H₂S adsorptive performance of NPCs is highly superior to that of non-doped porous carbon. X-rays photoelectron spectroscopy analyses combined with quantum chemical calculations demonstrate that the adsorption performance of the as-prepared NPCs depends on their nitrogen content and N-bonding configurations in the carbon materials, as well as their porosity. Pyridinic nitrogen doped carbon in NPCs have stronger interaction with H₂S compared to pyrrolic and graphitic nitrogen doped carbon. Based on the advantages of the developed porosity and abundant nitrogen functional groups, the saturated sorption capacities of 0.97–1.25 mmol H₂S/g can be achieved over NPCs at 25 °C under dry and anaerobic conditions.     

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