Evaluation of radish (Raphanus sativus L.) peroxidase activity after high-pressure treatment with carbon dioxide

The objective of this work was to assess the influence of compressed CO₂ on the specific activity of peroxidase (POD) from radish (Raphanus sativus L.). The protein concentrate, in phosphate buffer, was obtained through the precipitation of proteins with (NH₄)₂SO₄. The peroxidase activity was determined using guaiacol as substrate. A semi-factorial experimental design was adopted to evaluate the effects of temperature (30–50 °C), exposure time (1–6 h), carbon dioxide density (ρ_R = 0.6–1.8, resulting in pressures from 70.5 to 254.4 bar), and depressurization rate (10–200 kg/m³/min) on the peroxidase activity. Samples of lyophilized proteic concentrate were also submitted to high pressure and the effect of water content on the enzymatic activity in compressed CO₂ was studied. The water content in lyophilized samples was determined by thermo-gravimetric analysis. The results showed that the treatment of the enzymatic concentrate with CO₂ at high pressure could be a promising route to increase the POD activity.     

Liquefied petroleum gas as solvent medium for the treatment of immobilized inulinases

BACKGROUND: The main goal of this work is to assess the influence of pressurized liquefied petroleum gas (LPG) treatment on the enzymatic activity of immobilized inulinases. The effects of process variables were evaluated through 2³ experimental design. RESULTS: Inulinase from Klyveromyces marxianus NRRL Y‐7571 presented an increase of 163% in residual activity using LPG at 30 bar during 1 h exposure using a depressurization rate of 20 bar min^?1. For Aspergillus niger commercial inulinase, an increment of 129% in residual activity was observed at 30 bar for 1 h treatment at the highest depressurization rate (20 bar min^?1). Enzymatic activities changed significantly depending on the enzyme source and the experimental treatment conditions investigated, such as exposure time, depressurization rate and pressure. CONCLUSION: Hence, compressed LPG appears to be a promising technique with practical relevance as a preparation step to improve enzyme activity, thus helping the development of new biotransformation processes. © 2012 Society of Chemical Industry     

Thermal inactivation of airborne viable Bacillus subtilis spores by short-term exposure in axially heated air flow

In this investigation, an experimental facility was developed for quantifying the inactivation of viable bioaerosol particles in a controlled axially heated air flow. The tests were conducted with Bacillus subtilis var. niger endospores. The thermal inactivation of aerosolized spores was measured based on the loss of their culturability that resulted from a short-term exposure to air temperatures ranging from ～150 to >1000 °C. The cross-sectional and longitudinal temperature profiles in the test chamber were determined for different heating and flow conditions. The characteristic exposure temperature (T_e) was defined using a conservative approach to assessing the spore inactivation. Experimentally determined inactivation factors (IF) were corrected to account for the temperature profiles in the axially heated air flow. The reported IF-values serve as the lower approximation of the actual inactivation. Two data sets obtained at different flow rates, Q=18 and 36 L min^?1, represent different exposure conditions. In both cases, the thermal exposure of aerosolized spores produced no effect or only a moderate inactivation when the T_e remained below ～200 °C for 18 L min^?1 and ～250^oC for 36 L min^?1. The IF-values increased exponentially by about four orders of magnitude as the temperature rose by 150 °C. Depending on the flow rate, IF exceeded ～10⁴ at T_e>320 °C (Q=18 L min^?1) or >360 °C (Q=36 L min^?1). At T_e≈375–400 °C, the spore inactivation obtained at both flow rates reached the limit of quantification established in this study protocol, which translates to approximately 99.999% viability loss. The findings were attributed primarily to the heat-induced damage of DNA and denaturation of essential proteins. Up to a certain level of the thermal exposure, these damages are repairable; however, the self-repair capability diminishes as the heat rises and then the damage becomes totally irreversible. The data generated in this study provide an important reference point for thermal inactivation of stress-resistant spores in various biodefense/counterterrorism and air quality control applications.     

Lactose hydrolysis from milk/whey in batch and continuous processes by concanavalin A-Celite 545 immobilized Aspergillus oryzae β galactosidase

The present study deals with the immobilization of Aspergillus oryzae β galactosidase on concanavalin A layered Celite 545 as bioaffinity support. The activity yield of crosslinked enzyme was 71%. Michaelis constant, K_m was 2.45 mM and 5.58 mM for soluble and crosslinked adsorbed β galactosidase, respectively. V_max for soluble and crosslinked adsorbed enzyme was 0.52 mM/min and 0.38 mM/min, respectively. Moreover, Ki_app value of crosslinked β galactosidase was 366 × 10^?6 M while its soluble counterpart exhibited lower Ki_app value, 181 × 10^?6 M at 2% galactose concentration. Soluble and immobilized β galactosidase exhibited same pH and temperature optima at pH 4.5 and 50 °C. The crosslinked adsorbed enzyme retained 90% activity after 1 month of storage at 4 °C and 71% activity after its seventh repeated use. Moreover, crosslinked β galactosidase showed greater resistance to product inhibition mediated by glucose and galactose. Crosslinked Con A-Celite adsorbed β galactosidase showed increased efficiency in hydrolyzing lactose from milk and whey in batch processes at 50 °C as compared to the adsorbed and soluble enzyme. The hydrolysis of lactose in the continuous reactors containing crosslinked β galactosidase was 92% and 81% at flow rate of 20 mL h^?1 and 30 mL h^?1 after 1 month of operation, respectively.     

Comparison of the rate of CO2 absorption into aqueous ammonia and monoethanolamine

Aqueous ammonia has been proposed as an absorbent for use in CO₂ post combustion capture applications. It has a number of advantages over MEA such as high absorption capacity, low energy requirements for CO₂ regeneration and resistance to oxidative and thermal degradation. However, due to its small molecular weight and large vapour pressure absorption must be carried at low temperature to minimise ammonia loss. In this work the rate of CO₂ absorption into a falling thin film has been measured using a wetted-wall column for aqueous ammonia between 0.6 and 6 mol L^?1, 278–293 K and 0–0.8 liquid CO₂ loading. The results were compared to 5 mol L^?1 MEA at 303 and 313 K. It was found that the overall mass transfer coefficient for aqueous ammonia was at least 1.5–2 times smaller than MEA at the measured temperatures. From determination of the second-order reaction rate constant k₂ (915 L mol^?1 s^?1 at 283 K) and activation energy E_a (61 kJ mol^?1) it was shown that the difference in mass transfer rate is likely due to both the reduced temperature and differences in reactivity between ammonia and MEA with CO₂.     

Preparation and characterization of BaCe0.95Tb0.05O3−α hollow fibre membranes for hydrogen permeation

BaCe_0.95Tb_0.05O_3?α (BCTb) perovskite hollow fibre membranes were fabricated by spinning the slurry mixture containing 66.67 wt% BCTb powder, 6.67 wt% polyethersulphone (PESf) and 26.67 wt% N-methyl-2-pyrrolidone (NMP) followed by sintering at elevated temperatures. The influence of sintering temperature on the membrane properties was investigated in terms of crystal phase, morphology, porosity and mechanical strength. In order to obtain gas-tight hollow fibres with sufficient mechanical strength, the sintering temperature should be controlled between 1350 and 1450 °C. Hydrogen permeation through the BCTb hollow fibre membranes was carried out between 700 and 1000 °C using 50% H₂–He mixture as feed on the shell side and N₂ as sweep gas in the fibre lumen. The measured hydrogen permeation flux through the BCTb hollow fibre membranes reached up to 0.422 μmol cm^?2 s^?1 at 1000 °C when the flow rates of the H₂–He feed and the nitrogen sweep were 40 mL min^?1 and 30 mL min^?1, respectively.     

Extraction of sunflower oil with supercritical CO2: Experiments and modeling

Extraction of sunflower oil from sunflower seeds (Heliantus annuus L.) using supercritical CO₂ was studied. The shrinking core model was applied to the modeling of the packed-bed extraction process. The experimental data were obtained for extraction conducted at the pressures of 20, 30, 40, 50 and 60 MPa; the temperatures of 313, 333 and 353 K, the CO₂ flow rates of 1–4, and 6 cm³ CO₂ min⁻¹; the mean particle diameters of 0.23, 0.55, 1.09, 2.18 mm. The supercritical CO₂ extraction process was modeled by a quasi steady state model as a function of extraction time, pressure, temperature, CO₂ flow rate, and particle diameter. The supercritical CO₂ extraction process. The intraparticle diffusion coefficient (effective diffusivity) D_e was used as adjustable parameter. The model using the best fit of D_e was correlated the data satisfactorily.     

Ultrasound assisted synthesis of Gd and Nd doped ceria electrolyte for solid oxide fuel cells

In this study, the ceramic powders of Ce_1?xGd_xO_2?x/2 and Ce_1?xNd_xO_2?x/2 (x=0.05, 0.10, 0.15, 0.20 and 0.25) were synthesized by ultrasound assisted co-precipitation method. The ionic conductivity was studied as a function of dopant concentration over the temperature range of 300–800 °C in air, using the impedance spectroscopy. The maximum ionic conductivity, σ_800 °C=4.01×10^?2 Scm^?1 with the activation energy, E_a=0.828 kJmol^?1 and σ_800 °C=3.80×10^?2 Scm^?1 with the activation energy, E_a=0.838 kJmol^?1 were obtained for Ce_0.90Gd_0.10O_1.95 and Ce_0.85Nd_0.15O_1.925 electrolytes, respectively. The average grain size was found to be in the range of 0.3–0.6 μm for gadolinium doped ceria and 0.2–0.4 μm for neodymium doped ceria. The uniformly fine crystallite sizes (average 12–13 nm) of the ultrasound assisted prepared powders enabled sintering of the samples into highly dense (over 95%) ceramic pellets at 1200 °C (5 °C min^?1) for 6 h.     

New morphological Ba0.5Sr0.5Co0.8Fe0.2O3−α hollow fibre membranes with high oxygen permeation fluxes

Perovskite Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3?α (BSCF) hollow fibre membranes were fabricated by a combined phase inversion and sintering technique. The membranes were characterised by XRD, SEM and tested for air separation. The membrane possesses a novel morphology consisting of one dense layer and one porous layer. Oxygen permeation fluxes through the obtained hollow fibre membranes were measured in the temperature range 650–950 °C using helium sweep gas rates from 50 to 200 mL min^?1. Experimental results indicated the oxygen permeation flux through the BSCF hollow fibre membrane sintered at 1050 °C was approximately 11.46 mL min^?1 cm^?2 at 950 °C when the helium sweep rate was kept at 200 mL min^?1. The BSCF hollow fibre membrane showed a stable oxygen permeation flux of 8.60 mL min^?1 cm^?2 over the investigated period of 120 h at 900 °C.     

Preparation of sulfur-doped microporous carbons for the storage of hydrogen and carbon dioxide

Structurally well ordered, sulfur-doped microporous carbon materials have been successfully prepared by a nanocasting method using zeolite EMC-2 as a hard template. The carbon materials exhibited well-resolved diffraction peaks in powder XRD patterns and ordered micropore channels in TEM images. Adjusting the synthesis conditions, carbons possess a tunable sulfur content in the range of 1.3–6.6 wt.%, a surface area of 729–1627 m² g^?1 and a pore volume of 0.60–0.90 cm³ g^?1. A significant proportion of the porosity in the carbons (up to 82% and 63% for surface area and pore volume, respectively) is contributed by micropores. The sulfur-doped microporous carbons exhibit isosteric heat of hydrogen adsorption up to 9.2 kJ mol^?1 and a high hydrogen uptake density of 14.3 × 10^?3 mmol m^?2 at ?196 °C and 20 bar, one of the highest ever observed for nanoporous carbons. They also show a high CO₂ adsorption energy up to 59 kJ mol^?1 at lower coverages (with 22 kJ mol^?1 at higher CO₂ coverages), the highest ever reported for any porous carbon materials and one of the highest amongst all the porous materials. These findings suggest that S-doped microporous carbons are potential promising adsorbents for hydrogen and CO₂.     

Selective separation of low concentration CO2 using hydrogel immobilized CA enzyme based hollow fiber membrane reactors

This paper reported the results of developing a novel hollow fiber membrane reactor contained immobilized enzyme for selective separation of low concentration CO₂ from mixed gas streams. In the reactor, two bundles of poly(vinylidene fluoride) (PVDF) hollow fiber membranes were aligned staggered parallel in a tube module, and lab-made poly(acrylic acid-co-acrylamide)/hydrotalcite (PAA-AAm/HT) nanocomposite hydrogel was filled between fibers, in which carbonic anhydrase (CA enzyme) was immobilized. The effects of CA concentration, buffer concentration, the flow rate of sweep gas, operational temperature, and CO₂ concentration on separation performance were investigated in detail. The results showed that the transport resistance was mainly from the hydrogel layer, and decreased greatly with immobilization of carbonic anhydrase in hydrogel. Moreover, immobilized CA could retain over 76% enzymatic activity and thermal stability was also improved. The data showed that this enzyme-based membrane reactor could effectively separate CO₂ at low concentration from mixed gas streams. For the feed with 0.1% (v/v) of CO₂, the selectivity of CO₂/N₂ was 820, CO₂/O₂ was 330, and CO₂ permeance was 1.65×10^?8 mol/m² s Pa. Prolonged runs lasting 30 h showed that separation performances of the membrane reactor were quite stable.     

Micromechanisms of solid electrolyte interphase formation on electrochemically cycled graphite electrodes in lithium-ion cells

The microstructural and compositional changes that occurred in the solid electrolyte interphase (SEI) formed on graphite electrodes subjected to voltammetry tests (vs. Li/Li⁺) at different voltage scan rates were investigated. The microstructure of the SEI layer, characterized using high-resolution transmission electron microscopy, consisted of an amorphous structure incorporating crystalline domains of ～5–20 nm in size. Evidence of lithium compounds, namely Li₂CO₃ and Li₂O₂, and nano-sized graphite fragments was found within these crystalline domains. The morphology and thickness of the SEI depended on the applied voltage scan rate (dV/dt). The variations in the Li⁺ diffusion coefficient (D_Li⁺) at the electrode/electrolyte interface during the SEI formation process were measured and two regimes were identified depending on the scan rate; for dV/dt ≥ 3.00 mV s^?1, D_Li⁺ was 3.13 × 10^?8 cm² s^?1. At lower scan rates where D_Li⁺ was low, 0.57 × 10^?8 cm² s^?1, a uniform and continuous SEI layer with a tubular morphology was formed whereas at high dV/dt, the SEI formed had a columnar morphology and did not provide a uniform coverage.     

Visual and Raman spectroscopic observations of hot compressed water oxidation of guaiacol in fused silica capillary reactors

Using fused silica capillary reactors (FSCRs), we investigated the decomposition of guaiacol during hot compressed water oxidation (HCWO), with H₂O₂ added in stoichiometric ratios from 100 to 300%. Reactions were performed between 180 and 300 °C for durations from 2 to 10 min while the concurrent generation of CO₂ during the oxidation process was followed by Raman spectroscopy and the phase behavior of guaiacol in HCW, with or without H₂O₂, was observed visually under a polarized microscope configured with a heating/cooling stage. We found that complete conversion of guaiacol and 100% yield of CO₂ were achieved with a 150% stoichiometric ratio of oxidizer after 10 min at 200 and 300 °C, respectively. Based on the global reaction kinetics for the complete conversion of guaiacol to CO₂, the reaction is considered to be first order. The activation energy and pre-exponential factor for CO₂ formation are 18.62 kJ mol⁻¹ and 12.81 s⁻¹, respectively.     

Fungal fucoidanase production by solid-state fermentation in a rotating drum bioreactor using algal biomass as substrate

Fucoidanase enzymes able to degrade fucoidan were produced by solid-state fermentation (SSF). The fermentation assays were initially carried out in a laboratory-scale rotating drum bioreactor, and two fungal strains (Aspergillus niger PSH and Mucor sp. 3P) and three algal substrates (untreated, autohydrolyzed, and microwave processed seaweed Fucus vesiculosus) were evaluated. Additionally, fermentations were carried out under rotational (10 rpm) and static conditions in order to determine the effect of the agitation on the enzyme production. Agitated experiments showed advantages in the induction of the enzyme when compared to the static ones. The conditions that promoted the maximum fucoidanase activity (3.82 U L^?1) consisted in using Mucor sp. 3P as fungal strain, autohydrolyzed alga as substrate, and the rotational system. Such conditions were subsequently used in a 10 times larger scale rotating drum bioreactor. In this step, the effect of controlling the substrate moisture during the enzyme production by SSF was investigated. Moreover, assays combining the algal substrate with an inert support (synthetic fiber) were also carried out. Fermentation of the autohydrolyzed alga with the moisture content maintained at 80% during the fermentation with Mucor sp. 3P gave the highest enzyme activity (9.62 U L^?1).     

Uptake of chloride and carbonate ions by calcium monosulfoaluminate hydrate

Decommissioning of old nuclear reactors may produce waste streams containing chlorides and carbonates, including radioactive ³⁶Cl^? and ¹⁴CO₃^2?. Their insolubilization by calcium monosulfoaluminate hydrate was investigated. Carbonates were readily depleted from the solution, giving at thermodynamic equilibrium monocarboaluminate, monocarboaluminate + calcite, or calcite only, depending on the initial ratio between the anion and calcium monosulfoaluminate hydrate. Chloride ions reacted more slowly and were precipitated as Kuzel's salt, Kuzel's and Friedel's salts, or Friedel's salt only. Rietveld refinement of X-Ray powder diffraction patterns was successfully used to quantify the phase distributions, which were compared to thermodynamic calculations. Moreover, analysing the lattice parameters of Kuzel's salt as a function of its chloride content showed the occurrence of a restricted solid solution towards the sulfate side with general formula 3CaO·Al₂O₃·xCaCl₂·(1 ? x)CaSO₄·(12 ? 2x)·H₂O (0.36 ≤ x ≤ 0.50).     

Electrodeposited hybrid films of polyaniline and manganese oxide in nanofibrous structures for electrochemical supercapacitor

Hybrid films of polyaniline (PANI) and manganese oxide (MnO_x) were obtained through potentiodynamic deposition from solutions of aniline and MnSO₄ at pH 5.6. The hybrid films demonstrated characteristic redox behaviors of PANI in acidic aqueous solution. Characterization of the hybrid films by XRD indicated the amorphous nature of MnO_x in the films in which manganese existed in oxidation states of +2, +3 and +4, based on XPS measurement. Hybrid film of PANI and MnO_x, PM120 obtained from the solution of 0.1 M aniline and 120 mM Mn²⁺ displayed a well opened nanofibrous structure which showed an 44% increase in specific capacitance from that of PANI (408 F g^?1) to 588 F g^?1, measured at 1.0 mA cm^?2 in 1 M NaNO₃ (pH 1). The hybrid film kept more than 90% of its capacitance after 1000 charging-discharging cycles, with a coulombic efficiency of 98%. The specific capacitance of a symmetric capacitor using PM120 as the electrodes is 112 F g^?1.     

Synthesis and adsorption studies of novel hybrid mesoporous copolymer functionalized with protoporphyrin for batch and on-line solid-phase extraction of Cd2+ ions

A hybrid copolymer [poly(ethylene glycol dimethacrylate-co-protoporphyrin)-silica], synthesized by free radical copolymerization and sol–gel process was evaluated as novel adsorbent for solid-phase extraction of Cd²⁺ ions. Characterization of hybrid polymer was performed by FTIR, SEM and surface area analyzes. Adsorption isotherms built at pH 8.9 were very well adjusted (R² = 0.9982) to hybrid non-linear Langmuir–Freundlich model for two sites, indicating the existence of different affinity constants for binding sites, which was confirmed by Scatchard plot. The estimated maximum adsorption capacity was found to be 8.28 mg g^?1. The adsorption kinetics data also corroborated to the isotherm, where the Cd²⁺ ions adsorption followed the pseudo-second-order kinetic (R² = 0.998). The on-line preconcentration procedure, optimized by means of factorial designs, was based on sample preconcentration (16 mL) at pH 8.9 through 50.0 mg of hybrid copolymer packed in mini-column at 8.0 mL min^?1 flow rate. The on-line desorption of Cd²⁺ ions towards the FAAS detector was carried out in countercurrent at 5.0 mL min^?1 flow rate using 0.8 mol L^?1 HNO₃. Using the on-line preconcentration procedure, the maximum adsorption capacity determined from breakthrough curve was found to be 2.25 mg g^?1. Analytical curve ranged from 0.0 up to 50.0 μg L^?1 (r = 0.997), limit of detection of 0.27 μg L^?1, preconcentration factor of 38.4, sample throughput of 30 h^?1 and consumptive index of 0.41 mL, were achieved. The preconcentration method, very tolerable to several foreign ions, was successfully applied to the Cd²⁺ ions determination in water samples and cigarette sample. The accuracy was checked from analysis of certified reference materials.     

Uranyl ion-selective optical test strip

A novel, optical sensor, test strip has been developed for the spectrophotometric determination of trace amounts of uranyl ions, UO₂²⁺, based on immobilization of C.I. Mordant Blue 29 (Chromazurol S)/cetyl N,N,N-trimethyl ammonium bromide ion pair on a triacetyl cellulose membrane. Optimization of the sensor for the detection of low levels of uranyl ion is described. The test strip responded linearly to uranyl ions between 3.0 × 10^?7 and 6.0 × 10^?5 mol L^?1; the reproducibility of the sensor at a medium level of UO₂²⁺ activity was ±0.55%. The optical sensor can be regenerated using 0.01 mol L^?1 HCl or 0.01 mol L^?1 NaF solution after 10 min. The developed test strip was used in the determination of UO₂²⁺ in ground water samples.     

Adsorption characteristics of a fully exchanged potassium chabazite zeolite prepared from decomposition of zeolite Y

In this work a comprehensive study was undertaken to characterize the porous nature of a fully exchanged potassium chabazite zeolite (KCHA) and evaluate its adsorption properties under different conditions. A synthetic chabazite was prepared from the decomposition of zeolite Y and ion-exchanged to produce a fully exchanged potassium chabazite with Si/Al ratio of 2.4. In addition, sodium chabazite (NaCHA) and lithium chabazite (LiCHA) were synthesized for comparison purposes. Equilibrium isotherms for N₂ and CO₂ were measured at 273 K for further characterization. Our results show that the porous structure characterization by N₂ at 77 K and Ar at 87 K following the standard methods of BET for surface area, t-plot, DR and DFT for pore size distribution and volume reveal pore blockage phenomenon with substantially diminished adsorption capacities. However, CO₂ adsorption capacity on KCHA at 273 K reveals magnitudes of 70.1% and 78.7% of those on LiCHA and NaCHA, and a DFT pore volume of 0.214 cm³ g^?1. The surface area of KCHA calculated from the CO₂ isotherm using the Tóth model in its revised form demonstrates a surface area of 584.4 m² g^?1. This is in contrast to 17.82 and 13.48 m² g^?1 obtained from the BET model using N₂ and Ar at 77 and 87 K, respectively. It was concluded that the reliability of standard methods (viz. BET using N₂ at 77 K) for characterizing these particular porous solids is questionable under certain circumstances leading to misevaluation of adsorbent properties.     

Development of electrochemical cell with layered composite of the Gd-doped ceria/electronic conductor system for generation of H2–CO fuel through oxidation–reduction of CH4–CO2 mixed gases

This paper shows the recent results on the development of layered composite promoting two types of electrochemical reactions (oxidation and reduction) in one cell. This cell consisted of porous Ni–Gd-doped (GDC) ceria cathode/thin porous GDC electrolyte (50 μm)/porous SrRuO₃–GDC anode. The external electric current was flowed in this cell at the electric field strength of 1.25 and 6.25 V/cm. The mixed gases of CH₄ (30–70%) and CO₂ (70–30%) were fed at the rate of 50 ml/min to the cell heated at 400–800 °C under the electric field. In the cathode, CO₂ was reduced to CO (CO₂ + 2e^? → CO + O^2?) and the formed CO and O^2? ions were transported to the anode through the pores and surface and interior of grains of GDC film. On the other hand, CH₄ was oxidized in the anode to form CO and H₂ through the reaction with diffusing O^2? ions (CH₄ + O^2? → CO + 2H₂ + 2e^?). As a result, H₂–CO mixed fuel was produced from the CH₄–CO₂ mixed gases (CH₄ + CO₂ → 2H₂ + 2CO). This electrochemical reaction proceeded completely at 800 °C and no blockage of gases was measured for long time (>10 h). Only H₂–CO fuel was generated in the wide gas compositions of starting CH₄–CO₂ gases.