Reaction selectivity of <Emphasis Type="Italic">Burkholderia cepacia</Emphasis> (PS-30) lipase as influenced by monoacylation of <Emphasis Type="Italic">sn</Emphasis>-glycerol

Reaction selectivities were determined in multicompetitive reactions mediated by Burkholderia cepacia lipase (Amano PS-30) at a water activity of 0.19 in hexane. Saturated FA (C4–C18 even chain) and oleic acid (C18∶1) were reacted with a single alcohol, glycerol, α-or β-MAG, containing C4, C10, C16, or C18∶1 individually as alcohol cosubstrate. Similar odrinal patterns of FA selectivity, with C8, C10, and C16 preferred over others, were generally observed for incorporation of FA into specific acylglycerol (AG) pools of the 24 specific cases evaluated. The three exceptions were enrichment of C14 and C18 in the MAG pool with α-C16-MAG, substrate, and a general suppression of >C8 incorporation into the TAG pool for reactions with α-C10- and α-C16-MAG. PS-30 lipase selectivity toward MAG was in descending order: α/β-C4-MAG>β-C10-MAG>β-C16-MAG>α/β-C18∶1-MAG>α-C10-MAG>α-C16-MAG. Selectivity in channeling CX of the original CX-MAG substrates into higher AG species was in descending order: α-C10-MAG∼α-C16-MAG>α-C18∶1-MAG>β-C10-MAG∼β-C16-MAG∼β-C18∶1-MAG >α/β-C4-MAG. Generally, MAG were better acyl donors than FA for esterification reactions leading to DAG formation. These observations are relevant to the design of biocatalytic processes intended to yield specifically structured TAG.     

Application of microfiltration systems coupled with powdered activated carbon to river water treatment

A bench scale submerged microfiltration system coupled with high concentration of PAC (powdered activated carbon) was applied in order to purify a river water containing secondary effluent. The system was operated with four different modes: Run-1, -2, -3 and -4. The PAC concentration was set at 0, 4 and 40 g/L with same filtration rate of 1.0 m/d (42 L/m²/h) which correspond to Run-1, -2 and -3. In Run-4, the filtration rate was set at 0.5 m/d (21 L/m²/h) with PAC concentration of 40 g/L. The effluent turbidity showed below 0.1 NTU for all runs, and the removal rates more than 90% were observed. As for TOC removal, almost no removal of TOC was observed in Run-1 while the higher removal rates were obtained with the higher dosage of powdered activated carbon. Run-3 and 4 with PAC dose of 40 g/L showed the removal of 85% regardless of the filtration rates. Removal of UV254 was similar to that of TOC: removal of 13% at Run-1 and 90% at Run-3 and -4. As for the filtration efficiency, an average filtration time for TMP to reach 60 kPa was checked for each runs. The filtration time of around 5 days was observed in Run-1 and Run-2, 2 days in Run-3 and 60 days in Run-4. According to the results, the effluent water quality got better with higher dose of PAC and the filtration efficiency was enhanced with higher dose of PAC and lower filtration time.     

A QM/MM study of the catalytic mechanism of aspartate ammonia lyase

Aspartate ammonia lyase (Asp) is one of three types of ammonia lyases specific for aspartate or its derivatives as substrates, which catalyzes the reversible reaction of l-aspartate to yield fumarate and ammonia. In this paper, the catalytic mechanism of Asp has been studied by using combined quantum-mechanical/molecular-mechanical (QM/MM) approach. The calculation results indicate that the overall reaction only contains two elementary steps. The first step is the abstraction of C_β proton of l-aspartate by Ser318, which is calculated to be rate limiting. The second step is the cleavage of C_αN bond of l-aspartate to form fumarate and ammonia. Ser318 functions as the catalytic base, whereas His188 is a dispensable residue, but its protonation state can influence the active site structure and the existing form of leaving amino group, thereby influences the activity of the enzyme, which can well explain the pH dependence of enzymatic activity. Mutation of His188 to Ala only changes the active site structure and slightly elongates the distance of C_β proton of substrate with Ser318, causing the enzyme to remain significant but reduced activity.     

A comprehensive approach to evaluating watershed models for predicting river flow regimes critical to downstream ecosystem services

Selection of strategies that help reduce riverine inputs requires numerical models that accurately quantify hydrologic processes. While numerous models exist, information on how to evaluate and select the most robust models is limited. Toward this end, we developed a comprehensive approach that helps evaluate watershed models in their ability to simulate flow regimes critical to downstream ecosystem services. We demonstrated the method using the Soil and Water Assessment Tool (SWAT), the Hydrological Simulation Program–FORTRAN (HSPF) model, and Distributed Large Basin Runoff Model (DLBRM) applied to the Maumee River Basin (USA). The approach helped in identifying that each model simulated flows within acceptable ranges. However, each was limited in its ability to simulate flows triggered by extreme weather events, owing to algorithms not being optimized for such events and mismatched physiographic watershed conditions. Ultimately, we found HSPF to best predict river flow, whereas SWAT offered the most flexibility for evaluating agricultural management practices.     

Synthesis and swelling properties of poly[acrylamide-co-(crotonic acid)] superabsorbents

Superabsorbent polymers of acrylamide (AAm)/crotonic acid (CA) were synthesized by foamed polymerization in an aqueous solution of AAm with CA as a comonomer, initiated by an initiator couple of ammonium persulfate and N,N,N′N′-tetramethylethylenediamine. A crosslinking agent N,N′-methylenebisacrylamide, a foaming agent sodium bicarbonate, and a foam stabilizer, a triblock copolymer of polyoxyethylene/polyoxypropylene/polyoxyethylene, were used in the polymerization. The influences of the relative contents of CA, crosslinking agent, and initiator, on the swelling properties of the superabsorbent polymer systems were examined. The superabsorbent polymer synthesized with an AAm/CA ratio of 98:2 by mole, 0.5 wt.% of N,N′-methylenebisacrylamide and 1 wt.% of ammonium persulfate at 250 rpm and 50 °C for 30 min of polymerization time produced the highest water absorption of 211 ± 9 times its dried weight and could absorb water up to 162 ± 4 g g⁻¹ of the dry copolymer within 10 min. The electrochemical reaction for acrylamide–crotonic acid polymerization was investigated by cyclic voltammetry. The anodic current indicated that acrylamide acting as an electron donor whereas crotonic acid performed as an electron receiver, then providing the cathodic current. The diffusion of water into the superabsorbent polymer was non-Fickian (case II and anomalous). Acrylamide–crotonic acid superabsorbents containing various crosslinker concentrations had a water swelling in the range of 79–289 g g⁻¹. The diffusion coefficients varied between 6.9 × 10⁻⁹ and 5.1 × 10⁻⁸ cm² s⁻¹. Adsorption of the basic dye by the superabsorbent was a monolayer evaluated by the Langmuir isotherm. The superabsorbents can thus be used to adsorb cationic dyes in textile industry.     

Vapour phase hydrogenation of phenol over Pd/C catalysts: A relationship between dispersion,metal area and hydrogenation activity

A series of palladium supported on activated carbon catalysts, with Pd varying from 0.5 to 6.0 wt%, were prepared via wet impregnation method using PdCl₂ · xH₂O as a precursor salt. The dried samples were further reduced at 573 K in hydrogen and characterized by CO adsorption at room temperature in order to determine the dispersion, metal area and particle size. The catalysts were tested for vapour phase phenol hydrogenation in a fixed-bed all glass micro-reactor at a reaction temperature of 453 K under normal atmospheric pressure. The decrease in metal surface area as well as dispersion with corresponding increase in turn-over frequency (TOF) against palladium loadings suggest the unusual inverse relationship that exist between Pd dispersion and phenol hydrogenation activity over Pd/carbon catalysts. The stability of TOF at larger crystallite size indicates that phenol hydrogenation is less sensitive reaction especially beyond 3 wt% of Pd content. It is evident from the results that structural properties of the catalysts strongly influence the availability of Pd atoms on the surface for CO chemisorption and hence for phenol hydrogenation. A comparison between selectivity and product yield of the reaction against overall phenol conversion indicates that changes in reaction selectivity for cyclohexanone or cyclohexanol is independent of phenol conversion level and either of the product is not formed at the cost of another. The stability of the catalysts with reaction time suggests that coke formation on the surface of the catalyst is less significant and the formation of cyclohexanone remains almost total even at higher reaction temperatures.     

酶法酯化脂肪酸与甘油合成1,3-甘油二酯

采用脂肪酶催化甘油和脂肪酸直接酯化合成1,3-甘油二酯(DAG).考察了3种不同脂肪酶、酶用量以及底物物质的量的比对合成1,3-DAG的影响.结果表明:最适条件为脂肪酶RM IM,用量为反应底物质量的5%,n(脂肪酸)∶n(甘油)=2.25∶1.在此条件下,分别采用正辛酸、月桂酸、棕榈酸、硬脂酸和油酸与甘油酯化合成1,3-DAG,反应产物经纯化后,均可得到高纯度(95%)的1,3-DAG.     

响应曲面法优化甘薯饮料配方的研究

以甘薯为实验材料,以甘薯浓缩汁、蔗糖、柠檬酸和甘薯香精为实验因素,利用响应曲面法进行实验设计,对甘薯饮料的最佳配方进行了研究,并对最佳配方进行了感官评价验证、理化指标检测和微生物学检测.通过对实验得到的回归方程和响应曲面分析得出甘薯饮料的最佳组合为100 mL饮料中甘薯浓缩汁1.28 mL,柠檬酸0.1 g,蔗糖5.41 g,甘薯香精2.84mL,感官评分为83.43.