Optimization of medium by orthogonal matrix method for submerged mycelial culture and exopolysaccharide production in Collybia maculata

Optimization of submerged culture conditions for the production of mycelial growth and exopolysaccharides (EPSs) by Collybia maculata was investigated. The optimum temperature and the initial pH for EPS production in a shake-flask culture of C. maculata were found to be 20°C and 5.5, respectively. Among the various medium’s constituents examined, glucose, Martone A-1, K₂HPO₄, and CaCl₂ were the most suitable carbon, nitrogen, and mineral sources for EPS production, respectively. The optimum concentration of the medium’s ingredients determined using the orthogonal matrix method was as follows: 30 g/L of glucose, 20 g/L of Martone A-1, 1g/L of K₂HPO₄, and 1g/L of CaCl₂. Under the optimized culture conditions, the maximum concentration of EPSs in a 5-L stirred-tank reactor was 2.4 g/L, which was approximately five times higher than that in the basal medium. A comparative fermentation result showed that the EPS productivity in an airlift reactor was higher than that in the stirred-tank reactor despite the lower mycelial growth rate. The specific productivities and the yield coefficients in the airlift reactor were higher than those in the stirred-tank reactor even though the volumetric productivities were higher in the stirred-tank reactor than in the airlift reactor.     

Kinetics of xylitol fermentation by Candida guilliermondii grown on rice straw hemicellulosic hydrolysate

The fermentation kinetics for the conversion of rice straw hemicellulosic hydrolysate to xylitol by the yeast Candida guilliermondii was evaluated under batch conditions. The fermentation was accomplished in a 1 L working volume stirred-tank reactor with aeration of 1.3 vvm and agitation of 300 rpm (k_La=15/h). The maximum specific rate of xylitol formation (0.12 g/g) was achieved when the specific growth rate was lowered to 1/5 of its highest value. From analysis of the fermentation kinetics, a linear correlation between specific growth rate (μ_x) and specific rate of xylitol formation (q_p) was evident. Based on the Gaden model, this bioprocess was classified as growth-associated production and the relationship between μ_x and q_p can be described by the equation q_p=6.31μ_x.     

Effect of agitation and aeration on production of hexokinase by Saccharomyces cerevisiae

A batch culture of Saccharomyces cerevisiae for the production of hexokinase was carried out in a 5-L fermentor containing 3 L of culture medium, which was in oculated with cell suspension (about 0.7 g/L), and left ferm entingat 35°C and pH 4.0. The aeration and agitation were adjusted to attain k _La values of 15, 60, 135, and 230 h⁻¹. The highest hexokinase productivity (754.6 U/[L h]) and substrate-cell conversion yield (0.21 g/g) occurred for a k _La of 60 h⁻¹. Moreover, the formation of hexokinase and cell growth are coupled events, which is in accordance with the constitutive character of this enzyme. Hexokinase formation for k _La>60 h⁻¹ was not enhanced probably owing to saturation of the respiratory pathway by oxygen.     

Study on photosensitized oxidative desulfurization of thiophene by riboflavin

Photosensitized oxidative desulfurization of thiophene in n-octane/water extraction system with riboflavin as photosensitizer and O₂ in air as oxidant was studied. A 500 W high pressure Hg lamp was used as the light source for irradiation and air was introduced by a gas pump for supplying O₂. The desulfurization yield of thiophene was 85.4% for a 3 h photoirradiation under the conditions with an air flow of 150 mL/min, water/oil ratio of 1:1 and riboflavin concentration of 30 μmol/L. The mechanism of photosensitized oxidation of thiophene is¹O₂ exited from ³O₂ by the addition of riboflavin. Under the above conditions, the photooxidation kinetics of thiophene with O₂/riboflavin is first-order with a rate constant of 0.3277 h⁻¹ and half-time of 1.37 h.     

Some engineering parameters for Propionic acid fermentation coupled with Ultrafiltration

The effect of circulation rate on permeate flux, the energy requirements for heating or cooling, the reactor homogeneity, and cell activity are discussed for a continuous culture system with cell recycle. The fermentation system was a continuous stirred-tank reactor with an ultrafiltration membrane unit for cell recycle. The membranes have a tubular configuration and are composed of a carbon support coated with zirconium oxide. The permeate flux obtained for a long-run fermentation with Propionibacterium acidi-propionici was higher when the circulation rate was increased: 5.13 L/m²-h for a circulation rate of 0.810 m³/h and 7.09 L/m²-h for 1.104 m³/h. The temperature rise inside the fermenter for different circulation rates was studied, allowing determination of the need of input or output of energy for temperature control. Residence time distribution studies showed that, with a circulation rate of 0.606 m³/h, the dead volume was 9.2%, whereas at 1.104 m³/h the reactor behavior was almost ideal. The influence of the circulation rate on loss of cell activity is also discussed, and rheological studies are suggested as an indirect indicator of cell viability. We hereby express our recognition for the ongoing collaborations with James Gaddy (University of Arkansas) and Gerard Goma (INSA, Toulouse, France).     

Co-Fermentation of Cheese Whey and Crude Glycerol in EGSB Reactor as a Strategy to Enhance Continuous Hydrogen and Propionic Acid Production

This study evaluated the production of hydrogen and propionic acid in an expanded granular sludge bed (EGSB) reactor by co-fermentation of cheese whey (CW) and crude glycerol (CG). The reactor was operated at hydraulic retention time (HRT) of 8 h by changing the CW/CG ratio from 5:1 to 5:2, 5:3, 5:4, and 5:5. At the ratio of 5:5, HRT was reduced from 8 to 0.5 h. The maximum hydrogen yield of 0.120 mmol H₂ g COD^?1 was observed at the CW/CG ratio of 5:1. Increasing the CG concentration repressed hydrogen production in favor of propionic acid, with a maximum yield of 6.19 mmol HPr g COD^?1 at the CW/CG ratio of 5:3. Moreover, by reducing HRT of 8 to 0.5 h, the hydrogen production rate was increased to a maximum value of 42.5 mL H₂ h^?1 L^?1at HRT of 0.5 h. The major metabolites were propionate, 1,3-propanediol, acetate, butyrate, and lactate.     

Granulation of activated sludge in a laboratory upflow sludge blanket reactor

The creation of anoxic granulated biomass has been monitored in a laboratory USB (Upflow Sludge Blanket) reactor with the volume of 3.6 L. The objective of this research was to verify the possibilities of post-denitrification of residual NO₃-N concentrations in treated wastewater (denitrification of 10-20 mg L⁻¹ NO₃-N) and to determine the maximum hydraulic and mass loading of the granulated biomass reactor. G-phase from biodiesel production and methanol were both tested as external organic denitrification substrates. The ratio of the organic substrate COD to NO₃-N was 6. Only methanol was proven as a suitable organic substrate for this kind of reactor. However, the biomass adaptation to the substrate took over a week. The cultivation of anoxic granulated biomass was reached at hydraulic loading of over 0.35 m h⁻¹. The size of granules was smaller when compared with results found and described in literary reports (granules up to 1 mm); however, settling properties were excellent and denitrification was deemed suitable for the USB reactor. Sludge volume indexes of granules ranged from 35-50 mL g⁻¹ and settling rates reached 11 m h⁻¹. Maximum hydraulic and mass loadings in the USB reactor were 0.95 m3 m⁻² h⁻¹ and 6.6 kg m⁻³ d⁻¹. At higher loading levels, a wash-out of the biomass occurred. Presented at the 35th International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 26–30 May 2008.     

Production of the Biopesticide Azadirachtin by Hairy Root Cultivation of Azadirachta indica in Liquid-Phase Bioreactors

Batch cultivation of Azadirachta indica hairy roots was carried out in different liquid-phase bioreactor configurations (stirred-tank, bubble column, bubble column with polypropylene basket, and polyurethane foam disc as root supports) to investigate possible scale-up of the A. indica hairy root culture for in vitro production of the biopesticide azadirachtin. The hairy roots failed to grow in the conventional bioreactor designs (stirred tank and bubble column). However, modified bubble column reactor (with polyurethane foam as root support) configuration facilitated high-density culture of A. indica hairy roots with a biomass production of 9.2 g l^?1dry weight and azadirachtin yield of 3.2 mg g^?1 leading to a volumetric productivity of azadirachtin as 1.14 mg l^?1 day^?1. The antifeedant activity in the hairy roots was also evaluated by no choice feeding tests with known concentrations of the hairy root powder and its solvent extract separately on the desert locust Schistocerca gregaria. The hairy root powder and its solvent extract demonstrated a high level of antifeedant activity (with an antifeedant index of 97 % at a concentration of 2 % w/v and 83 % at a concentration of 0.05 % (w/v), respectively, in ethanol).     

Long-Term Stable Hydrogen Production from Water and Lactic Acid via Visible-Light-Driven Photocatalysis in a Porous Microreactor

Photocatalytic hydrogen (H₂) production is significant to overcome challenges like fossil fuel depletion and carbon dioxide emission, but its efficiency is still far below that which is needed for commercialization. Herein, we achieve long-term stable H₂ bubbling production from water (H₂O) and lactic acid via visible-light-driven photocatalysis in a porous microreactor (PP12); the catalytic system benefits from photocatalyst dispersion, charge separation, mass transfer, and dissociation of O−H bonds associated with H₂O. With the widely used platinum/cadmium-sulfide (Pt/CdS) photocatalyst, PP12 leads to a H₂ bubbling production rate of 602.5 mmol h⁻¹ m⁻², which is 1000 times higher than that in a traditional reactor. Even when amplifying PP12 into a flat-plate reactor with an area as large as 1 m² and extending the reaction time to 100 h, the H₂ bubbling production rate still remains at around 600.0 mmol h⁻¹ m⁻², offering great potential for commercialization.     

Optimization of Lactic Acid Production by Pellet-Form Rhizopus oryzae in 3-L Airlift Bioreactor Using Response Surface Methodology

The influence of two key environmental factors, pH and oxygen transfer coefficient (k _La), was evaluated on the lactic acid production as the main answer and, on the size of cell pellets of the fungal strain Rhizopus oryzae KPS106, as second dependant answer by response surface methodology using a central composite design. The results of the analysis of variance and modeling demonstrated that pH and k _La had a significant effect on lactic acid production by this strain. However, no interaction was observed between these two experimental factors. pH and k _La had no significant influence on the pellet size. Optimal pH and k _La of the fermentation medium for lactic acid production from response surface analysis was 5.85 and of 3.6 h^?1, respectively. The predicted and experimental lactic acid maximal values were 75.4 and 72.0 g/l, respectively, with pellets of an average of 2.54?±?0.41 mm. Five repeated batches in series were conducted with a mean lactic acid production of 77.54 g/l. The productivity was increased from 0.75 in the first batch to 0.99 g/l h in the last fifth batch.     

Removal of Nitrogen and Organic Matter in a Radial-Flow Aerobic-Anoxic Immobilized Biomass Reactor Used in the Posttreatment of Anaerobically Treated Effluent

This work reports on the removal of organic matter and nitrogen in a radial-flow aerobic-anoxic immobilized biomass (RAIB) reactor fed with domestic sewage pretreated in a horizontal-flow anaerobic immobilized biomass (HAIB) reactor. Polyurethane foam was used as support material for biomass attachment in both reactors. In batch experiments, a first-order kinetic model with residual concentration represented the organic matter removal rate, whereas nitrogen conversion followed a pseudo-first-order reaction in series model, with kinetic constants k ₁ (ammonium to nitrite) and k ₂ (nitrite to nitrate) of 0.25 and 6.62 h⁻¹, respectively. The RAIB reactor was operated in continuous-flow mode and changes in the airflow rate and hydraulic retention time were found to interfere in the apparent kinetic constants to the nitritation (k ₁) and nitratation (k ₂). Nitrification and denitrification were achieved in the partially aerated RAIB reactor operating with hydraulic retention times of 3.3 h and 2.7 h in the aerobic and anoxic zones, respectively. Ethanol was added in the anoxic zone of the reactor to promote denitrification. The effluent flow of the RAIB reactor presented a COD of 52 mg l⁻¹, and concentrations of 2 mg , 1.24 mg and 3.46 mg .     

Vibrational spectra of icosahedral (Ih and I) fullerenes

On the bases of the topological structures of the three big classes of icosahedral fullerenes: (1) C_n(I_h, n=60h²; h=1, 2,…), (2) C_n(I_h, n=20h²; h=1, 2,…), and (3) C_n(I, n=20(h²+hk+k²), h>k; h, k=1, 2,…), we derived formulas for the decomposition of their nuclear motions into irreducible representations. Hence, we obtained the infrared and Raman active modes for all of the icosahedral (I_h and I) fullerenes theoretically. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 66 : 113–117, 1998     

Electrochemical investigations of the reaction mechanism and kinetics between NADH and riboflavin immobilised on amorphous zirconium phosphate

Electrochemical investigations of the reaction mechanism and kinetics between riboflavin immobilised on zirconium phosphate (ZPRib) in carbon paste and NADH showed results yielding reliable information about aspects on the mechanism of the electron transfer reaction between the flavin and NADH. The formal potential (E°′) of the adsorbed riboflavin was −220 mV versus SCE at pH 7.0. A shift about 250 mV towards a more positive potential compared with its value in solution was assigned to the interaction between the basic nitrogen of riboflavin and the acid groups of ZP. The invariance of the E°′ with the pH of the contacting solution and the effect of different buffer constituents were attributed to the protection effect of ZP over the riboflavin. The electrocatalytic oxidation of NADH at the electrode was investigated using cyclic voltammetry and rotating disk electrode methodology using a potential of −50 mV versus SCE. The heterogeneous electron transfer rate constant, k _obs, was 816 M⁻¹ s⁻¹ and the Michaelis-Menten constant, K _M, was 1.8 mM (confirming a charge transfer complex intermediate in the reaction) for an electrode with a riboflavin coverage of 6.8 × 10⁻¹⁰ mol cm⁻². This drastic increase in the reaction rate between NADH and the immobilised riboflavin was assigned to the shift of the E°′. A surprising effect with addition of calcium or magnesium ion to the solution was also observed. The E°′ was shifted to −150 mV versus SCE and the reaction rate for NADH oxidation increased drastically. Received: 22 February 1999 / Accepted: 10 March 1999     

Vibration spectra and NMR spectra of octahedral (Oh and O) fullerenes

On analyzing the topological structures of the three big types of octahedral fullerenes: (1) C_n(O_h, n=24h²; h=1, 2,…); (2) C_n(O_h, n=8h²; h=1, 2,…), and (3) C_n(O, n=8(h²+hk+k²); h>k, h, k=1, 2,…), we have obtained theoretically the infrared and Raman active modes by means of the derived formulas for the decomposition of their nuclear motions into irreducible representations and the NMR spectra by using the distribution functions for all of the octahedral (O_h and O) fullerenes, respectively. ©1999 John Wiley & Sons, Inc. Int J Quant Chem 72: 199–205, 1999     

Formation of NO from N2/O2 Mixtures in a Flow Reactor: Toward an Accurate Prediction of Thermal NO

We have conducted flow reactor experiments for NO formation from N₂/O₂ mixtures at high temperatures and atmospheric pressure, controlling accurately temperature and reaction time. Under these conditions, atomic oxygen equilibrates rapidly with O₂. The experimental results were interpreted by a detailed chemical model to determine the rate constant for the reaction N₂ + O ? NO + N (R1). We obtain k₁ = 1.4 × 10¹⁴ exp(?38,300/T) cm³ mol^?1 s^?1 at 1700–1800 K, with an error limit of ±30%. This value is 25% below the recommendation of Baulch et al. for k₁, while it corresponds to a value k_1b of the reverse reaction 25% above the Baulch et al. evaluation. Combination of our results with literature values leads to a recommended rate constant for k_1b of 9.4 × 10¹² T^0.14 cm³ mol^?1 s^?1 over 250–3000 K. This value, which reconciles the differences between the forward and reverse rate constant, is recommended for use in kinetic modeling.     

Measurement of the neutron activation constants Q 0 and k 0 for the 27Al(n, γ)28Al reaction at the JSI TRIGA Mark II reactor

Measurements of the neutron activation constants Q ₀ and k ₀ for the ²⁷Al(n, γ)²⁸Al reaction have been performed in two irradiation channels with different spectral characteristics at the JSI TRIGA Mark II reactor. In the determination of Q ₀ the fission spectrum contribution to the reaction rates has been corrected for. The final experimental value of the Q ₀ factor was found to differ significantly from the adopted value in the k ₀-database. The experimental value of the k ₀ factor is in agreement with the recommended value in the k ₀-database. The thermal cross-section and resonance integral for the reaction were found to be in good agreement with the values calculated from the cross-sections from the ENDF/B-VII.1 library.     

Multienzymatic Sucrose Conversion into Fructose and Gluconic Acid through Fed-Batch and Membrane-Continuous Processes

Multienzymatic conversion of sucrose into fructose and gluconic acid was studied through fed-batch and continuous (in a membrane reactor) processes. The law of substrate addition (sucrose or glucose) for the fed-batch process which led to a yield superior to 80% was the decreasing linear type, whose feeding rate (?; L/h) was calculated through the equation: ? = ?_o ? k.t, where ?_o (initial feeding rate, L/h), k (linear addition constant, L/h ²), and t (reaction time, h). In the continuous process, the yield of conversion of sucrose (Y) was superior to 70% under the following conditions: dilution rate?=?0.33 h^?1, total duration of 15 h, pH 5.0, 37 °C and initial sucrose concentration of 64 g/L (Y?=?92%), 100 g/L (Y?=?83%), or 150 g/L (Y?=?76%).     

Deuterium isotope effect in the T1 → S0 radiationless transition of propynal in the gas phase

The phosphorescence lifetimes of propynal-h₁ and propynal-d₁ have been measured at room temperature in the 40 mTorr-1 Torr pressure range The reciprocal of the zero-pressure lifetime (k₀) is (3.10 ± 0.05) × 10³ and (1.70 ± 0.04) × 10³ s^?1 for propynal-h₁ and propynal-d¹ For both compounds the rate constant for self-quenching between triplet and ground-state molecules is k_SQ = (1 2±007) × 10³ Torr^?1 s^?1 The deuterium isotope effect is attributed to the T₁ → S₀ radiationlcss decay, for which k^H_ISC/k^D_ISC = 2 4     

Butanol production by Clostridium beijerinckii BA101 in an immobilized cell biofilm reactor

Acetone butanol ethanol was produced in a continuous immobilized cell (biofilm) plug-flow reactor inoculated with Clostridium beijerinckii BA101. To achieve high reactor productivity, C. beijerinckii BA101 cells were immobilized by adsorption onto clay brick. The continuous plug-flow reactor offers high productivities owing to reduced butanol inhibition and increased cell concentration. Although high productivity was achieved, it was at the expense of low sugar utilization (30.3%). To increase sugar utilization, the reactor effluent was recycled. However, this approach is complicated by butanol toxicity. The effluent was recycled after removal of butanol by pervaporation to reduce butanol toxicity in the reactor. Recycling of butanolfree effluent resulted in a sugar utilization of 100.7% in addition to high productivity of 10.2g/(L·h) at a dilution rate of 1.5 h⁻¹. A dilution rate of 2.0h⁻¹ resulted in a reactor productivity of 16.2g/(L·h) and sugar utilization of 101.4%. It is anticipated that this reactor-recovery system would be economical for butanol production when using C. beijerinckii BA101.     

Kinetic Study of Hydrogen–Deuterium Exchange of Glutamic Acid in Deuterated Hydrochloric Acid Solution

The kinetics of the hydrogen–deuterium (H–D) exchange at both the methine (alpha) and methylene (gamma) positions of glutamic acid in deuterated hydrochloric acid solution has been studied in the temperature range of 383–433 K by ¹H NMR detection. The reaction rates of H–D exchange at the two positions were described by applying multivariable linear regression (MLR) analysis and are determined as v = k[Glu]^3.3[D₃O⁺]^1.5 mol L^?1 h^?1 with k = 3.52 × 10¹⁶ × exp (–1.37 × 10⁵/RT) mol^?3.8 L h^?1 for the alpha position as well as v = k[Glu]^1.0[D₃O⁺]^0.45 mol L^?1 h^?1 with k = 1.77 × 10¹² × exp (–0.99 × 10⁵/RT) mol^?0.45 L h^?1 for the gamma position. The Arrhenius activation energy (E_a) at the gamma position is less than that at the alpha position, which implies that the deuteration reaction at the gamma position proceeded more easily.