Amidination of lipase with hydrophobic imidoesters

Lipase fromCandida rugosa was chemically modified by amidination with imidoester hydrochlorides of different hydrophobicity. The modified enzyme showed a higher ester synthesis activity but a lower ester hydrolysis activity compared with the native enzyme. The maximum specific activity of the modified enzyme depended on its degree of derivatization. Benzene was found to be the best solvent for the synthesis reaction. The optimal temperature for the reaction was not affected by modification of the lipase. The modified lipase was more thermostable and solvent-stable than the native enzyme. When fatty acids of different carbon chainlength were tested as substrates in the synthesis of esters with the modified lipase, the highest activity was observed with myristic acid and propanol.     

Solid contents of palm‐based biofuel mixtures with respect to storage and handling

The solid content (SC) of biofuel mixtures obtained from mixing crude palm oil (CPO) with medium fuel oil (MFO), and refined palm oil (RPO) with petroleum diesel (PD), was investigated. The SC of these mixtures will impact on their applications, storage and handling. The concentrations of CPO and RPO in the investigated mixtures ranged from 5 to 90% for the CPO‐MFO system and from 0 to 10% for the RPO‐PD system. For CPO/MFO mixtures, their SC exhibited eutectic behavior over the temperature range measured (5–20 °C). Eutectic minima were observed in the 80–90% CPO concentration range for all temperatures. These eutectic minima are due to dilution effects and the formation of van der Waals hydrogen bonds between the asphaltenes in MFO and the triacylglycerols. RPO/PD mixtures did not show any eutectic behavior. The SC for the RPO/PD mixtures were observed to be below 4% at 5 °C after 24 h of tempering and 0% at 15 °C over the same tempering period. When semi‐solid, ambient PO is used as a biofuel, heating is required to liquify it for ease of handling. When mixed with petroleum‐based fuels in the correct proportion, present handling and storage equipment and facilities are adequate for handling these mixtures.     

Combination of Oxyanion Gln114 Mutation and Medium Engineering to Influence the Enantioselectivity of Thermophilic Lipase from Geobacillus zalihae

The substitution of the oxyanion Q114 with Met and Leu was carried out to investigate the role of Q114 in imparting enantioselectivity on T1 lipase. The mutation improved enantioselectivity in Q114M over the wild-type, while enantioselectivity in Q114L was reduced. The enantioselectivity of the thermophilic lipases, T1, Q114L and Q114M correlated better with log p as compared to the dielectric constant and dipole moment of the solvents. Enzyme activity was good in solvents with log p < 3.5, with the exception of hexane which deviated substantially. Isooctane was found to be the best solvent for the esterification of (R,S)-ibuprofen with oleyl alcohol for lipases Q114M and Q114L, to afford E values of 53.7 and 12.2, respectively. Selectivity of T1 was highest in tetradecane with E value 49.2. Solvents with low log p reduced overall lipase activity and dimethyl sulfoxide (DMSO) completely inhibited the lipases. Ester conversions, however, were still low. Molecular sieves employed as desiccant were found to adversely affect catalysis in the lipase variants, particularly in Q114M. The higher desiccant loading also increased viscosity in the reaction and further reduced the efficiency of the lipase-catalyzed esterifications.     

Modeling and optimization of lipase‐catalyzed synthesis of dilauryl adipate ester by response surface methodology

BACKGROUND: Adipate esters are used as low‐temperature and low‐viscosity plasticizers for polyvinyl chloride and its copolymers. In this work, optimization of lipase‐catalyzed production of dilauryl adipate was carried out using response surface methodology (RSM) based on a four‐factor‐five‐level central composite rotatable design (CCRD). Immobilized lipase from Candida antarctica (Novozym 435) was used as catalyst in this reaction. Various reaction parameters affecting the synthesis of adipate ester, including alcohol/acid molar ratio, amount of enzyme, temperature and reaction time, were investigated. RESULTS: Statistical analysis showed that the amount of enzyme was less significant than the other three factors. The optimal conditions for the enzymatic reaction were obtained at 5.7:1 substrate molar ratio using 0.18 g of enzyme at 53.1 °C for 282.2 min. Under these conditions the esterification percentage was 96.0%. CONCLUSIONS: The results demonstrated that response surface methodology can be applied effectively to optimize the lipase‐catalyzed synthesis of adipate ester. The optimum conditions can obtained be used to scale up the process. Copyright © 2008 Society of Chemical Industry     

Direct liquid fuel cells: A review

Direct liquid fuel cells (DLFCs) are one of the most promising types of fuel cells due to their high energy density, simple structure, small fuel cartridge, instant recharging, and ease of storage and transport. Alcohols such as methanol and ethanol were the most common types of fuel used, although glycols and acids are also used. The main problem that arose in direct liquid fuel cells (DLFCs) was the high cost of the catalyst and the high catalyst loading. Other issues, such as fuel crossover, cathode flooding, the generation of various side products, fuel safety and unproven long-term durability, must also be solved to improve the performance of DLFCs. More research studies were required to increase its performance and foster commercialization. Currently, there were some commercial products using direct methanol fuel cells (DMFCs) and direct ethanol fuel cells (DEFCs), but the other types of DLFCs were generally still in the research stage. This paper aims to review the different types of liquid fuels directly used in fuel cells and identify their properties, challenges and applications.     

Equilibrium headspace analysis of volatile flavor compounds extracted from soursop (Annona muricata) using solid-phase microextraction

The influence of headspace solid-phase microextraction (HS-SPME) variables, namely, sample concentration, salt concentration and sample amount, on the equilibrium headspace analysis of the main volatile flavor compounds released from soursop was investigated. A total of 35 volatile compounds, comprising 19 esters, six alcohols, three terpenes, two acids, two aromatics, two ketones and an aldehyde, were identified. The results indicated that all response-surface models were significantly (p < 0.05) fitted for 10 target volatile flavor compounds. The results further indicated that more than 65% of the variation in the equilibrium headspace concentrations of target volatile flavor compounds could be explained by the final reduced models, with high R² values ranging from 0.658 to 0.944. Multiple optimization results showed that extraction using a 76.6% (w/w) sample concentration, 20.2% (w/w) salt and 8.2 g of blended soursop pulp was predicted to provide the highest overall equilibrium headspace concentration for the target soursop volatile flavor compounds.     

Studies on fouling by natural organic matter (NOM) on polysulfone membranes: Effect of polyethylene glycol (PEG)

Polysulfone membranes were prepared via phase inversion technique by using polyethylene glycol with molecular weights of 400, 1500 and 6000 Da as pore forming agent in dope formulation. The performance of membrane was characterized using humic acid and water sample taken from Sembrong River, Johor, Malaysia was used as natural organic matter sources. Membrane properties were also characterized in terms of mean pore radius, pure water flux, humic acid rejection and fouling resistance. The results indicated that the pure water flux and mean pore radius of membranes increased with the increase of PEG content. Fourier transform infrared spectroscopy results revealed the presence of hydrophilic component in PSf/PEG blend with the significant appearance of O–H peak at 3418.78 cm^− 1. Scanning electron microscopy analysis revealed the presence of finger-like structure for all membranes and the structure intensified as PEG content was increased. The results obtained from the fouling study indicated that the membrane with the lowest PEG content and molecular weight has an excellent performance in mitigating fouling.     

Silver-filled polyethersulfone membranes for antibacterial applications — Effect of PVP and TAP addition on silver dispersion

Silver-filled asymmetric polyethersulfone (PES) membranes were prepared by a simple phase inversion technique. The effects of polyvinylpyrrolidone (PVP) and 2, 4, 6-triaminopyrimidine (TAP) on the surface properties of the silver-filled asymmetric membrane were investigated for antibacterial application. The dispersion of silver nanoparticles (Ag) and silver content on membrane surface were characterized using field emission scanning electron microscope (FESEM) and energy dispersive spectrometer (EDS), respectively. Results showed that smaller silver particles were formed in PES membranes when PVP and TAP were added during dope preparation. Using inductively coupled plasma mass spectrometry (ICP-MS), it is found that silver leaching has been significantly reduced up to 57% and 63% upon the addition of PVP and TAP respectively. The improved silver dispersion on membrane surfaces was able to enhance the antibacterial activity against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) as evidenced by larger inhibition ring in agar diffusion method. The filtration of E. coli suspension (optical density = 0.31 at λ = 600 nm) carried out on prepared membranes proved that PES-AgNO₃ with TAP as dispersant appeared to inhibit almost 100% bacterial growth in rich medium. Hence, overall results showed the potential of PES-AgNO₃ with TAP to be used for antibacterial applications especially in water treatment.     

Improved Water Level Forecasting Performance by Using Optimal Steepness Coefficients in an Artificial Neural Network

Developing water level forecasting models is essential in water resources management and flood prediction. Accurate water level forecasting helps achieve efficient and optimum use of water resources and minimize flooding damages. The artificial neural network (ANN) is a computing model that has been successfully tested in many forecasting studies, including river flow. Improving the ANN computational approach could help produce accurate forecasting results. Most studies conducted to date have used a sigmoid function in a multi-layer perceptron neural network as the basis of the ANN; however, they have not considered the effect of sigmoid steepness on the forecasting results. In this study, the effectiveness of the steepness coefficient (SC) in the sigmoid function of an ANN model designed to test the accuracy of 1-day water level forecasts was investigated. The performance of data training and data validation were evaluated using the statistical index efficiency coefficient and root mean square error. The weight initialization was fixed at 0.5 in the ANN so that even comparisons could be made between models. Three hundred rounds of data training were conducted using five ANN architectures, six datasets and 10 steepness coefficients. The results showed that the optimal SC improved the forecasting accuracy of the ANN data training and data validation when compared with the standard SC. Importantly, the performance of ANN data training improved significantly with utilization of the optimal SC.     

Completion energies and scale

The detection of smooth curves in images and their completion over gaps are two important problems in perceptual grouping. We examine the notion of completion energy of curve elements, showing, and exploiting its intrinsic dependence on length and width scales. We introduce a fast method for computing the most likely completion between two elements, by developing novel analytic approximations and a fast numerical procedure for computing the curve of least energy. We then use our newly developed energies to find the most likely completions in images through a generalized summation of induction fields. This is done through multiscale procedures, i.e., separate processing at different scales with some interscale interactions. Such procedures allow the summation of all induction fields to be done in a total of only O(N log N) operations, where N is the number of pixels in the image. More important, such procedures yield a more realistic dependence of the induction field on the length and width scales: the field of a long element is very different from the sum of the fields of its composing short segments.