Application of a two‐stage temperature control strategy to enhance 1,3‐propanediol productivity by Clostridium butyricum

BACKGROUND: The purpose of the present work was to enhance 1,3‐propanediol productivity during the batch cultivation on a type of raw glycerol by application of a two‐stage temperature control strategy. RESULTS: First, the effect of the raw glycerol on microbial growth and 1,3‐propanediol production was investigated. The highest 1,3‐propanediol productivity, 1.93 g L^?1 h^?1, was achieved when the initial raw glycerol concentration was 6% (v/v). Second, the effect of temperature on microbial growth and 1,3‐propanediol production was investigated and kinetic analysis was carried out. The results indicated that 37 °C favored microbial growth while 35 °C was best for 1,3‐propanediol production. Finally, a two‐stage temperature control strategy was applied in 1,3‐propanediol production. The incubation temperature was kept at 37 °C from inoculation to 2 h and then switched to 35 °C. Compared with batch cultivations at 35 and 37 °C, the fermentation time was shortened from 10 to 9.2 h, resulting in an increase in 1,3‐propanediol productivity of around 11%. CONCLUSION: 1,3‐propanediol productivity was enhanced effectively by application of a two‐stage temperature control strategy. © 2012 Society of Chemical Industry     

Downstream processing of 1,3‐propanediol fermentation broth

The downstream processing of 1,3‐propanediol fermentation broth using flocculation, reactive extraction, and reactive distillation was studied. Cellular debris and soluble protein in the broth were flocculated by combined use of chitosan and polyacrylamide at optimal concentrations of 150 ppm and 70 ppm, respectively; the soluble protein in the broth decreased to 0.06 g L^?1, and the recovery ratio of the supernatant liquor to broth was greater than 99%. 1,3‐Propanediol and other alcohols were extracted from the supernatant liquor by reacting with butyraldehyde. In a four‐stage countercurrent extraction with the volume ratio of the extraction solvent to the aqueous phase being 20:100, more than 99% 1,3‐propanediol acetal (2‐propyl‐1,3‐dioxane) and 2,3‐butanediol acetal (2‐propyl‐4,5‐dimethyl‐1,3‐dioxolane) were recovered from the aqueous phase; 35% of the glycerol acetals were recovered. The acetals produced were hydrolyzed in a reactive distillation column using the strongly acidic cation‐exchange resin as catalyst, the bottom product obtained was a mixture of 1,3‐propanediol (407 g L^?1), 2,3‐butanediol (252 g L^?1), glycerol (277 g L^?1), and glycerol acetals (146 g L^?1). Copyright © 2005 Society of Chemical Industry     

Over‐expression of glycerol dehydrogenase and 1,3‐propanediol oxidoreductase in Klebsiella pneumoniae and their effects on conversion of glycerol into 1,3‐propanediol in resting cell system

BACKGROUND: Glycerol dehydrogenase [EC.1.1.1.6] and 1,3‐propanediol oxidoreductase [EC.1.1.1.202] were proved to be two of the key enzymes for glycerol conversion to 1,3‐propanediol in Klebsiella pneumoniae under anaerobic conditions. For insight into their significance on 1,3‐propanediol production under micro‐aerobic conditions, these two enzymes were over‐expressed in K. pneumoniae individually, and their effects on conversion of glycerol into 1,3‐propanediol in a resting cell system under micro‐aerobic conditions were investigated. RESULTS: In the resting cell system, over‐expression of 1,3‐propanediol oxidoreductase led to faster glycerol conversion and 1,3‐propanediol production. After a 12 h conversion process, it improved the yield of 1,3‐propanediol by 20.4% (222.1 mmol L⁻¹ versus 184.4 mmol L⁻¹) and enhanced the conversion ratio of glycerol into 1,3‐propanediol from 50.8% to 59.8% (mol mol⁻¹). Over‐expression of glycerol dehydrogenase in K. pneumoniae had no significant influence both on 1,3‐propanediol yield and on the conversion ratio of glycerol into 1,3‐propanediol in the resting cell system. CONCLUSION: The results were important for an understanding of the significance of glycerol dehydrogenase and 1,3‐propanediol oxidoreductase in 1,3‐proanediol production under micro‐aerobic conditions, and for developing better strategies to improve 1,3‐propanediol yield. Copyright © 2008 Society of Chemical Industry     

The effect of raw glycerol concentration on the production of 1,3‐propanediol by Clostridium butyricum

Raw glycerol, the main by‐product of the bio‐diesel production process, was converted to 1,3‐propanediol by Clostridium butyricum F2b. In batch cultures, 47.1 g dm^?3 of 1,3‐propanediol were produced. Continuous cultures were conducted at a constant dilution rate (= 0.04 h^?1) and various inlet glycerol concentrations with 1,3‐propanediol produced at levels up to 44.0 g dm^?3. At increasing glycerol concentrations in the inlet medium, biomass yield decreased. This decrease was attributed to the microbial metabolism being directed towards the biosynthesis of organic acids (and hence carbon losses as CO₂) instead of biochemical anabolic reactions. An autonomous analytical model was developed, and quantified the effect of inlet glycerol concentration on the production of biomass and metabolites. Indeed, high inlet substrate concentrations positively affected the biosynthesis, principally of butyric acid and to a lesser extent that of acetic acid. In contrast, at increased glycerol concentrations, the relative increase of 1,3‐propanediol production per unit of substrate consumed was lower as compared with that of acetic and, mainly, butyric acid. This could be explained by the fact that the butyric acid pathway represents an alternative and competitive one to that of 1,3‐propanediol for re‐generation of NADH₂ equivalents in the microbial cell. Copyright © 2004 Society of Chemical Industry     

Unstructured kinetic model for reuterin and 1,3‐propanediol production by Lactobacillus reuteri from glycerol/glucose cofermentation

BACKGROUND: Lactobacillus reuteri is unable to grow on glycerol as sole carbon and energy source hence, glycerol is used as an alternative hydrogen acceptor during growth on available carbohydrates. Thus, glycerol is converted to reuterin and 1,3‐propanediol (1,3‐PDL), both products with interesting industrial applications. These compounds are commonly produced by using resting cells in two‐step fermentation processes. RESULTS: The glycerol/glucose cofermentation by L. reuteri yields reuterin and 1,3‐PDL at a glycerol concentration higher than 100 mmol L⁻¹. An increase of glycerol concentration from 200 to 400 mmol L⁻¹ showed no additional stimulatory effect on ethanol and acetate production but consistently reduced the lactate concentration. It was also found that reuterin concentration reached a maximum value and subsequently decreased due to its conversion to 1,3‐PDL. An unstructured kinetic model was proposed to describe simultaneously microbial growth, substrates consumption and products formation. A multi‐response nonlinear regression analysis based on Marquardt algorithm combined with a Runge‐Kutta integration method was used to obtain the values of the fitting parameters. CONCLUSIONS: The optimum concentration of glycerol for maximum reuterin and 1,3‐PDL production was 200 mmol L⁻¹. The complete process was satisfactorily described by the kinetic model proposed. Copyright © 2008 Society of Chemical Industry     

Solvent‐free synthesis of glycerol carbonate and glycidol from 3‐chloro‐1,2‐propanediol and potassium (hydrogen) carbonate

BACKGROUND: An indirect solvent‐free synthetic approach for obtaining glycerol carbonate and glycidol from glycerol and CO₂ through their more reactive and easily synthesizable derivatives 3‐chloro‐1,2‐propanediol (HAL) and potassium (hydrogen) carbonate has been studied. RESULTS: The reaction is fast with source of carbonation and temperature having a strong influence on the results. A yield of 80% glycerol carbonate together with a simultaneous substantial production of glycidol (0.56 mol mol^?1 glycerol carbonate) are obtained using K₂CO₃ as the carbonation source at 80 °C, a reaction time of 30 min and a 3:1 HAL/K₂CO₃ molar ratio. A lower yield of glycerol carbonate (60%) is obtained from KHCO₃ after 50 min with the other experimental conditions remaining unchanged. In this case, glycidol formation is zero or insignificant. Glycerol is also obtained in high yields, although in much lower amounts from KHCO₃ (～0.59 mol mol^?1 glycerol carbonate independent of operating conditions) than from K₂CO₃ (0.84–1.1 mol mol^?1 glycerol carbonate, depending on experimental conditions). CONCLUSIONS: The proposed synthetic strategy overcomes the currently difficult direct reaction between glycerol and CO₂, leading to the simultaneous synthesis of two valuable chemicals: glycerol carbonate and glycidol. However, glycerol is also obtained in substantial amounts thus decreasing the overall yield of the process. Thus, methods for preventing its formation must be developed for industrial feasibility. Copyright © 2010 Society of Chemical Industry     

Optimization of 1,3‐propanediol production by novel recombinant Escherichia coli using response surface methodology

Response surface methodology was used to optimize 1,3-propanediol production by a novel recombinant Escherichia coli JM109 (pHsh-dhaB-yqhD). The optimal fermentation parameters for enhanced 1,3-propanediol yield were found to be: glycerol 61.8 g L⁻¹, yeast extract 6.2 g L⁻¹, Vitamin B₁₂ 0.049 g L⁻¹ and fermentation time 30 h. Subsequent experimental trials confirmed the validity of the model. These optimal fermentation conditions in the cultivation flask culture led to a 1,3-propanediol concentration of 43.1 g L⁻¹ and a conversion rate of 69.7% (g g⁻¹). A maximum 1,3-propanediol concentration of 41.1 g L⁻¹ was achieved in a 5 L fermenter using the optimized parameters. Copyright © 2006 Society of Chemical Industry     

2,4,6‐Trichlorophenol and phenol removal in methanogenic and partially‐aerated methanogenic conditions in a fluidized bed bioreactor

A fluidized bed bioreactor (FBBR) was operated for more than 575 days to remove 2,4,6‐trichlorophenol (TCP) and phenol (Phe) from a synthetic toxic wastewater containing 80 mg L^?1 of TCP and 20 mg L^?1 of Phe under two regimes: Methanogenic (M) and Partially‐Aerated Methanogenic (PAM). The mesophilic, laboratory‐scale FBBR consisted of a glass column (3 L capacity) loaded with 1 L of 1 mm diameter granular activated carbon colonized by an anaerobic consortium. Sucrose (1 g COD L^?1) was used as co‐substrate in the two conditions. The hydraulic residence time was kept constant at 1 day. Both conditions showed similar TCP and Phe removal (99.9 + %); nevertheless, in the Methanogenic regime, the accumulation of 4‐chlorophenol (4CP) up to 16 mg L^?1 and phenol up to 4 mg L^?1 was observed, whereas in PAM conditions 4CP and other intermediates were not detected. The specific methanogenic activity of biomass decreased from 1.01 ± 0.14 in M conditions to 0.19 ± 0.06 mmolCH₄ h^?1 gTKN^?1 in PAM conditions whereas the specific oxygen uptake rate increased from 0.039 ± 0.008 in M conditions to 0.054 ± 0.012 mmolO₂ h^?1 gTKN^?1, which suggested the co‐existence of both methanogenic archaea and aerobic bacteria in the undefined consortium. The advantage of the PAM condition over the M regime is that it provides for the thorough removal of less‐substituted chlorophenols produced by the reductive dehalogenation of TCP rather than the removal of the parent compound itself. Copyright © 2005 Society of Chemical Industry     

Synthesis and in vitro biological evaluation as antitumour drug carriers of folate‐targeted N‐isopropylacrylamide‐based nanohydrogels

Copolymeric nanohydrogels based on N‐isopropylacrylamide, N‐(pyridin‐4‐ylmethyl)acrylamide and tert‐butyl‐2‐acrylamidoethyl carbamate, synthesized by microemulsion polymerization, were characterized using Fourier transform infrared spectroscopy and their size (38–52 nm) determined using quasielastic light scattering. Folic acid was covalently attached to the nanohydrogels (1.40 ± 0.07 mmol g^?1). Tamoxifen (6.7 ± 0.2–7.3 ± 1.2 µg TMX mg^?1 nanohydrogel), a hydrophobic anticancer drug, and 5‐fluorouracil (7.7 ± 0.7–10.14 ± 1.75 µg 5‐FU mg^?1 nanohydrogel), a hydrophilic anticancer drug, were loaded into the nanohydrogels. Maximum in vitro TMX release (77–84% of loaded drug) depended on interactions of the drug with hydrophobic clusters of the nanogels; however, no nanogel/5‐FU interactions allowed total release of the loaded drug. The cytotoxicity of unloaded nanohydrogels in MCF7, T47D and HeLa cells was low. Cell uptake of nanogels without bound folic acid took place in the three cell types by unspecific internalization in a time‐dependent process. Cell uptake increased for folic acid‐targeted nanohydrogels in T47D and HeLa cells, which have folate receptors. The administration of 10 and 30 µmol L^?1 TMX by TMX‐loaded nanogels and 10 µmol L^?1 5‐FU by 5‐FU‐loaded nanogels was effective on the three cell types, and the best results were obtained for folic acid‐targeted nanohydrogels. Copyright © 2012 Society of Chemical Industry     

Time‐dependent dosing of Fe2+ for improved lipopeptide production by marine Bacillus megaterium

BACKGROUND: Lipopeptide production is strongly influenced by trace metals. The availability of free Fe²⁺ in the media throughout the process of fermentation was found to be very critical. Since free Fe²⁺ was reported to be sequestered by the lipopeptide as it was produced, intermittent feeding of Fe²⁺ was strategized and optimized for enhanced lipopeptide production by marine Bacillus megaterium in glucose mineral salts medium (GMSM). RESULTS: Studies with the single‐dose Fe²⁺ (0.48 mmol L^?1) supplementation after 8 h of fermentation resulted in lipopeptide concentration of 3.3 ± 0.1 g L^?1. Lipopeptide production was further enhanced to 4.2 ± 0.15 g L^?1 by adopting a multi‐dose Fe²⁺ feeding strategy. The maximum product yield (Y_P/S) of 0.24 ± 0.02 g g^?1 with specific product formation rate (q_p) of 0.124 ± 0.01 g g^?1 h^?1 was achieved when 0.48 mmol L^?1 Fe²⁺ was fed intermittently at different times as per the designed strategy. CONCLUSION: Lipopeptide concentration was improved 4.7‐fold by single‐dosing and 5.8‐fold by multiple dosing of Fe²⁺, when compared with GMSM without Fe²⁺ supplementation. Copyright © 2012 Society of Chemical Industry     

Production of organic solvent tolerant lipase by Staphylococcus caseolyticus EX17 using raw glycerol as substrate

BACKGROUND: In this work we used Plackett–Burman statistical design and central composite design in order to optimize culture conditions for lipase production by Staphylococcus caseolyticus strain EX17 growing on raw glycerol, which was obtained as a by‐product of the enzymatic synthesis of biodiesel. The stability of lipase was verified over several organic solvents, such as methanol, ethanol and n‐hexane. RESULTS: Optimal culture conditions for lipase production were found to be 36 °C, initial pH 8.12, glycerol 30 g L^?1, olive oil 3.0 g L^?1, and soybean oil 2.5 g L^?1, with 145.8 U L^?1 of enzyme activity. When commercial glycerol was substituted by the raw glycerol from biodiesel synthesis, lipolytic activity was 127.3 U L^?1. Experimental validation of enzyme production matched values predicted by the mathematical model, which was 138.3 U L^?1. Stability tests showed that lipase from S. caseolyticus EX17 was stable in methanol, ethanol, and n‐hexane. CONCLUSIONS: Results obtained in this work suggest that raw glycerol can be used for lipase production by S. caseolyticus EX17 and that this enzyme has a potential application in the synthesis of biodiesel. Copyright © 2008 Society of Chemical Industry     

Synthesis,solution properties and scale‐inhibiting behaviour of a diallylammonium/sulfur dioxide cyclocopolymer bearing phospho‐ and sulfopropyl pendents

Zwitterion (Z) monomer 3‐[diallyl{3‐(diethoxyphosphoryl)propyl}ammonio]propane‐1‐sulfonate underwent cyclocopolymerization with sulfur dioxide to give a new alternating copolymer poly(Z‐alt‐SO₂) in excellent yield (ca 90%). The polyzwitterion (±) (PZ) (i.e. poly(Z‐alt‐SO₂), bearing a diethylphosphonate as well as a sulfonate functionality in each repeat unit, upon ester hydrolysis gave its corresponding pH‐responsive polyzwitterionic acid (±) (PZA). The pH‐induced equilibrations (+) cationic polyelectrolyte ? (±) PZA ? polyzwitterion/anion (± ?) (PZAN) ? polyzwitterion/dianion (± =) (PZDAN) permitted us to examine the effects of charge types and their densities on the interesting solubility and viscosity behaviours. The apparent protonation constants of the basic functionalities &tbond;N^±PO₃^2? in (± =) PZDAN and &tbond;N^±PO₃H^1? in (± ?) PZAN in salt‐free water and 0.1 mol L^?1 NaCl were determined using potentiometric titrations. (±) PZA at a meagre concentration of 20 ppm was found to be an effective antiscalant to inhibit the precipitation of CaSO₄ from its supersaturated solution: after 500 and 800 min, the respective scale inhibitions of 86 and 98% indicated its potential use as an effective antiscalant in reverse osmosis plant. © 2014 Society of Chemical Industry     

Modelling aspects of the biotechnological valorization of raw glycerol: production of citric acid by Yarrowia lipolytica and 1,3‐propanediol by Clostridium butyricum

Raw glycerol, produced in significant quantities during several industrial processes, could be further considered as a potential substrate for microbial conversions. In the present report, modelling approaches are used in order to quantify the kinetic behavior of microorganisms capable of producing growth‐ and non growth‐associated metabolites when cultivated on raw glycerol. Citric acid production by Yarrowia lipolytica strain ACA‐DC 50109 was successfully simulated by Monod‐, Verhlust‐ and Williams‐type models, while the optimized parameter values were found to be similar to those experimentally measured. It has been demonstrated that the production of citric acid from raw glycerol, in terms of specific production rate and conversion yield, was similar or even better as compared with that obtained during cultivation of yeasts or molds on various conventional (eg sugar‐based) media. The production of 1,3‐propanediol by Clostridium butyricum strain F2b from raw glycerol was successfully simulated by a Contois‐type model. It was found that the maximum theoretical 1,3‐propanediol productivity was comparable with the highest one achieved during growth of various bacterial strains on pure glycerol in batch and continuous cultures. Raw glycerol could be used as an alternative substrate for citric acid and 1,3‐propanediol production, and possibly for other microbial products. Copyright © 2003 Society of Chemical Industry     

3,3′‐Diindolylmethane imprinted polymers: synthesis,characterization and analytical procedure for template isolation from biological matrix

A novel sorbent for the separation of 3,3′‐diindolylmethane (DIM) has been developed. DIM was used as a template molecule to prepare twelve imprinted polymers from seven different functional monomers in six various porogens in the presence of ethylene glycol dimethacrylate as a crosslinker. The binding capacity showed that the highest binding specificity was achieved when allylamine as the monomer and carbon tetrachloride as the porogen were used to form bulk polymers. Binding capacities were 130.4 ± 2.8 µg g^?1 for imprinted MIP7_a polymer versus 49.03 ± 0.44 µg g^?1 for non‐imprinted NIP7_a polymer. An imprinting factor of 3.12 reflected the high specificity of MIP7_a. A solid‐phase extraction protocol was fully optimized. Two methanol–water systems were selected as the most effective for loading and washing steps, while acetonitrile was chosen as the most efficient eluent suitable for recovery of 91.7 ± 3.8% of DIM. Optimal concentration of DIM and volume of loaded sample were also examined. A loaded volume of 2.5 mL was the most appropriate for 0.625 and 1.25 mg L^?1. The use of MIP7_a for the separations of DIM from spiked bovine serum albumin was evaluated, showing a total recovery of 87.7 ± 3.5%. The commercial sorbent C18 was not suitable for such an application. © 2013 Society of Chemical Industry     

Vinyl‐type homo‐ and copolymerization of norbornene catalyzed by bis(phenoxyimine) titanium complex

A ternary catalytic system consisting of a bis(phenoxyimine) titanium complex, triisobutylaluminium and an organoboron compound exhibited high activity in the vinyl‐type homopolymerization of norbornene. The obtained polynorbornene showed a modest molecular weight (M _n ≈ 5 × 10⁴ g mol^?1) and broad molecular weight distribution (polydispersity index ≈ 3.5). A copolymer of norbornene with 1,3‐butadiene was prepared using a binary catalytic system consisting of bis(phenoxyimine) titanium complex and triisobutylaluminium. The norbornene units in the copolymer adopted a vinyl‐type addition structure confirmed using distortionless enhancement by polarization transfer 135 ¹³C NMR microstructure analyses. Polymerization kinetics studies showed that neither monomer feed ratio nor conversion had an effect on the composition of the copolymer backbone which was composed of 55% norbornene units and 45% 1,3‐butadiene units. The essentially constant polymer composition implied an alternating nature of chain propagation. The copolymer exhibited good thermal stability and moderate glass transition temperature (50.9–68.2 °C) with a relatively high molecular weight (M _w = 0.18 × 10–1.31 × 10⁵ g mol^?1), and excellent transparency (maximal transmittance >80%). © 2017 Society of Chemical Industry     

Bio‐oxidation of ferrous ions by Acidithioobacillus ferrooxidans in a monolithic bioreactor

BACKGROUND: The bio‐oxidation of ferrous iron is a potential industrial process in the regeneration of ferric iron and the removal of H₂S in combustible gases. Bio‐oxidation of ferrous iron may be an alternative method of producing ferric sulfate, which is a reagent used for removal of H₂S from biogas, tail gas and in the pulp and paper industry. For practical use of this process, this study evaluated the optimal pH and initial ferric concentration. pH control looks like a key factor as it acts both on growth rate and on solubility of materials in the system. RESULTS: Process variables such as pH and amount of initial ferrous ions on oxidation by A. ferrooxidans and the effects of process variables dilution rate, initial concentrations of ferrous on oxidation of ferrous sulfate in the packed bed bioreactor were investigated. The optimum range of pH for the maximum growth of cells and effective bio‐oxidation of ferrous sulfate varied from 1.4 to 1.8. The maximum bio‐oxidation rate achieved was 0.3 g L^?1 h^?1 in a culture initially containing 19.5 g L^?1 Fe²⁺ in the batch system. A maximum Fe²⁺ oxidation rate of 6.7 g L^?1 h^?1 was achieved at the dilution rate of 2 h^?1, while no obvious precipitate was detected in the bioreactor. All experiments were carried out in shake flasks at 30 °C. CONCLUSION: The monolithic particles investigated in this study were found to be very suitable material for A. ferrooxidans immobilization for ferrous oxidation mainly because of its advantages over other commonly used substrates. In the monolithic bioreactor, the bio‐oxidation rate was 6.7 g L^?1 h^?1 and 7 g L^?1 h^?1 for 3.5 g L^?1 and 6 g L^?1 of initial ferrous concentration, respectively. For higher initial concentrations 16 g L^?1 and 21.3 g L^?1, bio‐oxidation rate were 0.9 g L^?1 h^?1 and 0.55 g L^?1 h^?1, respectively. Copyright © 2008 Society of Chemical Industry     

Time‐resolved small‐angle X‐ray scattering study of void fraction evolution in high‐density polyethylene during stress unloading and strain recovery

By means of time‐resolved small‐angle X‐ray scattering, we developed an analysis methodology to assess the void volume fraction ?_v in high‐density polyethylene (HDPE) during tensile testing. The specimens were first drawn up to different imposed strains, and subsequently were subjected to stress unloading and strain recovery stages. During the loading stage, ?_v progressively increased with the strain level, starting from a well‐defined onset strain prior to the yield point. In particular, ?_v reached a maximum of 8.75 vol% for a strain of 12.5% in the case of a HDPE grade with a molecular weight of 105 000 g mol^?1. Stress unloading and strain recovery caused a decrease in ?_v attained at the end of the loading stage. For a HDPE grade with a molecular weight of 55 000 g mol^?1, ?_v was more important during the loading stage and the decrease in ?_v was less marked during the stress unloading stage when compared to the HDPE with molecular weight of 105 000 g mol^?1. The residual and reversible components of void volume fraction were revealed. © 2015 Society of Chemical Industry     

Continuous production of 1,2‐propanediol by the selective hydrogenolysis of solvent‐free glycerol under mild conditions

BACKGROUND: The conversion of glycerol to value‐added derivatives is now critical, owing to the large surplus of glycerol from biodiesel production. The main objective of this work is to develop a novel process for converting solvent‐free glycerol to 1,2‐propanediol. RESULTS: Several catalysts were screened for aqueous‐phase hydrogenolysis of glycerol in an autoclave. The most effective catalysts (Ni/Al₂O₃, Cu/ZnO/Al₂O₃) were further tested for vapor phase hydrogenolysis in a fixed‐bed. Ni/Al₂O₃ did not prove as effective for the production of 1,2‐propanediol because of the high selectivity to CH₄ and CO. Over Cu/ZnO/Al₂O₃, glycerol was mainly converted to the desired 1,2‐propanediol and the reaction intermediate acetol. The production of 1,2‐propanediol was favoured at higher hydrogen pressure. At 190 °C and 0.64 MPa, near complete conversion of glycerol was achieved with 1,2‐propanediol selectivity up to 92%. In addition, a higher concentration (between 43.4% and 0.8%) of acetol was detected and an approximately stoichiometric relationship was found between acetol and 1,2‐propanediol. CONCLUSION: 1,2‐propanediol can be produced with high yields via the vapor phase hydrogenolysis of glycerol over Cu/ZnO/Al₂O₃. Furthermore, the mechanism of 1,2‐propanediol formation is suggested to proceed mainly through an acetol route over Cu/ZnO/Al₂O₃. Copyright © 2008 Society of Chemical Industry     

Study of the bio‐production of carotenoids by Sporidiobolus salmonicolor (CBS 2636) using pre‐treated agro‐industrial substrates

BACKGROUND: The increasing industrial demand for carotenoids has aroused interest in their bio‐production, and the need to reduce production costs has encouraged the use of low cost industrial substrates, such as agro‐industrial residues. Thus the objective of this research was the bio‐production of carotenoids by Sporidiobolus salmonicolor using agro‐industrial substrates (corn steep liquor and sugarcane molasses), pre‐treated with acids (sulphuric and phosphoric). RESULTS: Bio‐production was carried out in an orbital shaker using a 10% (v/v) inoculum, incubation at 25 °C, and agitation at 180 rpm for 120 h in a non‐illuminated environment. The carotenoids were recovered using liquid N₂ combined with dimethylsulphoxide for cell rupture, and an acetone/methanol mixture (7:3 v/v) for extraction. CONCLUSION: The complete second‐order design allowed for optimisation of the carotenoid concentration obtained from industrial substrates pre‐treated with acids (sulphuric and phosphoric), obtaining a total carotenoid content of 541.5 µg L^?1 using 10 g L^?1 sugarcane molasses, 5 g L^?1 corn steep liquor and 5 g L^?1 yeast hydrolysate at 25 °C, with agitation at 180 rpm and an initial pH of 4.0. Copyright © 2008 Society of Chemical Industry     

Kinetics and thermodynamics of glucoamylase inhibition by lactate during fermentable sugar production from food waste

BACKGROUND: Glucoamylase hydrolysis is a key step in the bioconversion of food waste with complicated composition. This work investigated the effect of lactate on glucoamylase from Aspergillus niger UV‐60, and inhibition mechanisms of glucoamylase by lactate during food waste hydrolysis. RESULTS: For 125 min hydrolysis of food waste (10%, dry basis), reducing sugars produced in the absence of lactate were 15%, 26% and 56% more than those produced in the presence of 24 g L^?1 lactate at 60, 50 and 40 °C, respectively. Kinetic study showed that the type of glucoamylase inhibition by lactate was competitive, and K_m (Michaelis‐Menten constent), V_max (maximum initial velocity), K_I (inhibition constant) were 103.2 g L^?1, 5.0 g L^?1 min^?1, 100.6 g L^?1, respectively, for food waste hydrolysis at 60 °C and pH 4.6. Lactate also accelerated glucoamylase denaturation significantly. Activation energy of denaturation without inhibitor was 61% greater than that of denaturation with inhibitor (24 g L^?1 lactate). Half‐lives (t_1/2) without inhibitor were 7.6, 2.7, 2.6, 1.7 and 1.2 times longer than those with inhibitor at temperature 40, 45, 50, 55 and 60 °C, respectively. CONCLUSION: These results are helpful to process optimization of saccharification and bioconversion of food waste. Copyright © 2010 Society of Chemical Industry