A continuous ultrasound‐assisted packed‐bed bioreactor for the lipase‐catalyzed synthesis of caffeic acid phenethyl ester

BACKGROUND: The focus of this paper is the ultrasound‐assisted synthesis of caffeic acid phenethyl ester (CAPE) from caffeic acid and phenyl ethanol in a continuous packed‐bed bioreactor. Immobilized Novozym^® 435 (from Candida antarctica) is used as the catalyst. A three‐level–three‐factor Box–Behnken design and a response surface methodology (RSM) are employed to evaluate the effects of temperature, flow rate, and ultrasonic power on the percentage molar conversion of CAPE. RESULTS: Based on ridge max analysis, it is concluded that the optimum condition for synthesis is reaction temperature 72.66 °C, flow rate 0.046 mL min^?1, and ultrasonic power 1.64 W cm^?2. The expected molar conversion value is 97.84%. An experiment performed under these optimal conditions resulted in a molar conversion of 92.11 ± 0.75%. The enzyme in the bioreactor was found to be stable for at least 6 days. CONCLUSIONS: The lipase‐catalyzed synthesis of CAPE by an ultrasound‐assisted packed‐bed bioreactor uses mild reaction conditions. Enzymatic synthesis of CAPE is suitable for use in the nutraceutical and food production industries. Copyright © 2011 Society of Chemical Industry     

Thermal decomposition kinetics of thermotropic copolyesters made from trans‐p‐hydroxycinnamic acid and p‐hydroxybenzoic acid

A series of thermotropic copolyesters were synthesized by direct thermal melt polycondensation of p‐acetoxybenzoic acid (PHB) with trans‐p‐acetoxycinnamic acid (PHC). The dynamic thermogravimetric kinetics of the copolyesters in nitrogen were analyzed by four single heating‐rate techniques and three multiple heating‐rate techniques. The effects of the heating rate, copolyester composition, degradation stage, and the calculating techniques on the thermostability and degradation kinetic parameters of the copolyesters are systematically discussed. The four single heating‐rate techniques used in this work include Friedman, Freeman–Carroll, Chang, and the second Kissinger techniques, whereas the three multiple heating‐rate techniques are the first Kissinger, Kim–Park, and Flynn–Wall techniques. The decomposition temperature of the copolyesters increases monotonically with increasing PHB content from 40 to 60 mol %, whereas their activation energy exhibits a maximal value at the PHB content of 50 mol %. The decomposition temperature, activation energy, the order, and the frequency factor of the degradation reaction for the thermotropic copolyester with PHB/PHC feed ratio of 50/50 mol % were determined to be 374°C, 408 kJ/mol, 7.2, and 1.25 × 10²⁹ min^?1, respectively. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 445–454, 2004     

Kinetics of the catalytic esterification of castor oil with lauric acid using <Emphasis Type="Italic">n</Emphasis>-butyl benzene as a water entrainer

The esterification of castor oil with lauric acid was investigated using tetra n-butyl titanate (TBT), SnCl₂·2H₂O (stannous chloride), CoCl₂·6H₂O (cobalt chloride), and (CH₃COO)₂Zn·2H₂O (zinc acetate dihydrate) as catalysts. Effects of catalyst concentration and reaction temperature on the progress of the reaction were investigated. TBT was the best catalyst for the esterification of castor oil with lauric acid at temperatures lower than 200°C. The reaction was first order with respect to each reactant. The activation energy for the esterification reaction of castor oil with lauric acid using TBT was 26.69 kcal/mol. The rate constants obtained for the esterification of castor oil with decanoic, lauric, palmitic, and stearic acids were nearly the same (15.80, 15.44, 15.06, and 14.67 mL mol⁻¹ min⁻¹), as were the rate constants obtained for the reaction of castor oil and hydrogenated castor oil.     

Immobilization of invertase onto dimer acid‐co‐alkyl polyamine

Invertase was immobilized onto the dimer acid‐co‐alkyl polyamine after activation with 1,2‐diamine ethane and 1,3‐diamine propane. The effects of pH, temperature, substrate concentration, and storage stability on free and immobilized invertase were investigated. Kinetic parameters were calculated as 18.2 mM for K_m and 6.43 × 10^?5 mol dm^?3 min^?1 for V_max of free enzyme and in the range of 23.8–35.3 mM for K_m and 7.97–11.71 × 10^?5 mol dm^?3 min^?1 for V_max of immobilized enzyme. After storage at 4°C for 1 month, the enzyme activities were 21.0 and 60.0–70.0% of the initial activity for free and immobilized enzyme, respectively. The optimum pH values for free and immobilized enzymes were determined as 4.5. The optimum temperatures for free and immobilized enzymes were 45 and 50°C, respectively. After using immobilized enzyme in 3 days for 43 times, it showed 76–80% of its original activity. As a result of immobilization, thermal and storage stabilities were increased. The aim of this study was to increase the storage stability and reuse number of the immobilized enzyme and also to compare this immobilization method with others with respect to storage stability and reuse number. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1526–1530, 2004     

Optimization of alkaline protease production from Shewanella oneidensis MR‐1 by response surface methodology

BACKGROUND: The proteases are among the most important groups of enzymes. Therefore, it is important to produce inexpensive and optimized media for large‐scale commercial production. In the present work, three different Shewanella species were screened on skim milk agar medium for their ability to produce alkaline protease. The effects of different culture conditions were optimized for alkaline protease production by S. oneidensis MR‐1 using a Box–Behnken design combined with response surface methodology (RSM). RESULTS: Highest yield (112.90 U mL^?1) of protease production was obtained at pH 9.0, a temperature of 30 °C, glucose (12.5 g L^?1), tryptone (12.5 g L^?1) and an incubation period of 36 h. A second‐order polynomial regression model was used for analysis of the experiment. The experimental values were in good agreement with predicted values, with correlation coefficient 0.9996. CONCLUSION: Carbon and nitrogen, pH, temperature and incubation period were chosen as the main factors to be used in an experimental design for optimization to produce low‐cost enzymes, potentially for use on an industrial scale. A 60% increase in enzyme activity was achieved in the optimized medium compared with the original medium. Copyright © 2008 Society of Chemical Industry     

pH‐Sensitive pectin polymeric rafts for controlled‐release delivery of pantoprazole sodium sesquihydrate

The aim of the present work was to develop pectin raft‐forming tablets for controlled‐release delivery of pantoprazole sodium sesquihydrate (PSS). A Box–Behnken design was used to optimize 15 formulations with three independent and three dependent variables. The physical tests of all compressed formulations were within pharmacopoeial limits. The rafts were characterized by their strength, thickness, resilience, reflux resistance, acid‐neutralizing capacity, floating lag time, and total floating time. The raft strength, thickness, resilience, and reflux resistance through a 10‐mm orifice of optimized formulation PR9 were 7.43 ± 0.019 g, 5.8 ± 0.245 cm, greater than 480 min, and 2490 ± 0.004 g, respectively. The buffering and neutralizing capacity was 11.2 ± 1.01 meq and 6.5 ± 0.56 meq, respectively. Dissolution studies were performed by using simulated gastric fluid at pH 1.2, and the cumulative percentage release of PR9 was found to be 97%. First‐order release kinetics were followed, and non‐Fickian diffusion was observed as the value of n was greater than 0.45 in the Korsmeyer–Peppas model. The Fourier transform infrared spectra of the PSS, polymers, and optimized raft formulation PR9 showed peaks at 3223.09 cm^?1, 1688.17 cm^?1, 1586.67 cm^?1, 1302.64 cm^?1, and 1027.74 cm^?1 that are due to ? OH stretching, ester carbonyl group (C?O) stretching, the existence of water and carboxylic groups in the raft, C? N stretching, and ? OH bending vibrations and showed no interaction between them. The developed raft was suitable for sustained‐release delivery of PSS. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44442.     

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     

Foaming Properties of Commercial Lauramide Amide Oxide in High‐Salinity Water

The original purpose of our work was finding commercial foaming agents for high‐salinity reservoirs. During the study, the commercial lauramide amide oxide solution displayed different foaming properties in high‐salinity water (salinity 220,000 mg/L) at different aging times and relatively low temperature (25 °C). Foam volume decreases drastically first with the increase of aging time. Then, with further aging, foam volume increases. However, in low‐salinity water or at high temperature, no obvious foam volume variation was observed. Lauric acid in the commercial surfactant plays a key role. Under proper temperature and pH conditions, lauric acid will react with Ca²⁺. Calcium laurate generated from lauric acid in the commercial form and Ca²⁺ from water influences the foaming property significantly. At the beginning of calcium laurate generation, surfactants adsorb on calcium laurate and decelerate the diffusion velocity of lauramide amide oxide from the bulk phase to the air–water interface. With the increase of aging time, calcium laurate gathers, thus adsorption of lauramide amide oxide by calcium laurate decreases. Hence, the foaming volume increases.     

Regioselective Synthesis of Palm-Based Sorbitol Esters as Biobased Surfactant by Lipase from Thermomyces lanuginosus in Nonaqueous Media

This paper describes the regioselective production of palm-based sorbitol monoesters via esterification catalyzed by Lipozyme^® TL IM (Thermomyces lanuginosus lipase adsorbed onto silica gel, Novozymes, Inc., Franklington, NC, USA). Effects of various reaction parameters including types of solvent, substrate molar ratio, molecular sieve and lipase concentration, temperature, reaction time, and fatty acid chain length were investigated. Approximately 76% conversion of sorbitol to sorbitol esters was achieved within 24 h under optimal conditions: sorbitol (0.4 M), fatty acid (0.8 M), 20 wt% Lipozyme^® TL IM in 100 mL tert-butanol at 55 °C for 24 h in the presence of 25 wt% 3 Å molecular sieve as water absorbent. The reactions were conducted in an orbital incubator shaker at a shaking rate of 200 rpm. Lipozyme^® TL IM was highly regioselective, esterifying exclusively at sorbitol's primary hydroxyl groups, producing 1-O- and 6-O-sorbitol monoesters. The biocatalyst also exhibited substrate selectivity toward shorter chain acyl donors, with caprylic acid exhibiting the highest conversion of sorbitol. In addition, Lipozyme^® TL IM was reused up to four successive reaction cycles without significant loss of activity. The biocatalytic process reported in this paper is a one-step process to produce biobased surfactants that does not involve the use of toxic or expensive solvents that are commonly employed for derivatization of sugars, or pre-derivatization of the substrates molecules.     

Lipase‐catalyzed synthesis of butyl esters by direct esterification in solvent‐free system

BACKGROUND: Reactions performed under solvent‐free conditions give processes that are environmentally friendly, since most solvents are polluting agents. In this work, the performance of Candida rugosa lipae (CRL) immobilized on styrene‐divinylbenzene (STY‐DVB) or controlled pore silica (CPS), and the commercial lipase Novozym 435, was evaluated for the synthesis of butyl esters in solvent–free systems (SFS). A 2² full factorial design was used to study the influence of the organic acid chain length and the biocatalyst concentration on the esterification performance. RESULTS: When CRL on STY‐DVB was used, the ester formation was influenced by both variables and their interaction. The reaction conversion was higher (63%) using 10% of immobilized system and lauric acid, corresponding to a productivity of 3.62 g L^?1 h^?1 For CRL on CPS, only the effect of biocatalyst concentration was significant, and the highest yield was attained using 20% of immobilized system and caprilic acid. In the case of Novozym 435, the highest yield (49%) was obtained using butyric acid as acyl donor at 15% of immobilized lipase. CONCLUSION: The results allowed better understanding of the influence of important parameters in this environmentally friendly process, which also has the process advantage of a higher volumetric productivity when compared with a solvent system. Copyright © 2007 Society of Chemical Industry     

Aspergillus oryzae Lipase-Catalyzed Synthesis of Dioleoyl; Palmitoyl-Rich Triacylglycerols in Two Reactors

Dioleoyl; palmitoyl‐rich triacylglycerols (OPO‐rich TAG) were synthesized through Aspergillus oryzae lipase (AOL)‐catalyzed acidolysis of palm stearin with commercial oleic acid by a one‐step process in a stirred tank reactor and continuous packed bed reactor to evaluate the feasibility of using immobilized AOL. AOL was found to be valuable for the synthesis of OPO‐rich TAG when compared with commercial lipase from Thermomyces lanuginose (Lipozyme^® TL IM; Novozymes A/S, Bagsvaerd, Denmark). The C52 (triglycerides with a carbon number of 52, stands for OPO, OPL, LPL and their isomers) content of AOL was higher (45.65 %), and the intensity of treatment (IOT: lipase amount × reaction time/TAG amount) of AOL was just 6.25 % of that of Lipozyme^® TL IM under similar reaction conditions in the stirred tank reactor. Response surface methodology were used to optimize the reaction conditions of the AOL‐catalyzed acidolysis is reaction in the packed bed reactor. The optimal point for the set of experimental conditions generated were as follows: residence time 3.0 h; temperature 62.09 °C; substrate molar ratio 7.13 mol/mol. The highest C52 content obtained was 48.60 ± 2.36 %, with 57.46 ± 1.72 % total palmitic acid at the sn‐2 position and 74.21 ± 2.45 % oleic acid at the sn‐1,3 positions. The half‐life of AOL was 24 h in the stirred tank reactor and 140 h in the packed bed reactor. The immobilized AOL achieved similar conversion and selectivity to commercial lipases for the catalyzed synthesis of OPO‐rich TAG and may offer a cheaper alternative.     

Enzymatic Interesterification Between Pine Seed Oil and a Hydrogenated Fat to Prepare Semi-Solid Fats Rich in Pinolenic Acid and Other Polyunsaturated Fatty Acids

Enzyme catalyzed interesterification (EIE) of pine seed oil (PSO) and a fully hydrogenated soybean oil (FHSBO) were studied in batch reactors in solvent-free media to prepare different semisolid fats rich in polyunsaturated fatty acids (PUFA). Optimal operation conditions found were: 10 % (w/w) enzyme loading, 75 °C and magnetic agitation at 300 rpm. Quasi-equilibrium conditions were reached after 2, 3 and 6 h, when immobilized lipases from Thermomyces lanuginosus (Lipozyme^® TL IM), Candida antarctica B. (Novozym^® 435) and Rhizomucor miehei (Lipozyme^® RM IM) from Novozymes A/S (Bagsvaerd, Denmark) were employed, respectively. Similar distributions of unsaturated to saturated fatty acid (UFA/SFA) residues along the glycerol backbone of the fat products were obtained with both non-selective and sn-1(3) regioselective lipases due to significant spontaneous acyl migration during the reaction. The products had higher UFA/SFA ratios at the sn-2 position (2.4–2.5, 1.4–1.7, and 0.5–0.8 for the trials involving 20, 40 and 70 % FHSBO, w/w, respectively) than the corresponding physical blends (0.8, 0.4 and 0.5, respectively). Fat products containing 3.1–11.6 % (w/w) pinolenic acid (Pn) and 16.1–35.7 % (w/w) linoleic acid (L) at the sn-2 position were prepared. The free acid contents of EIE products prepared with Lipozyme^® TL IM and Novozym^® 435 were 6.1–6.4 and 2.5–2.6, respectively. Residual activities of Lipozyme^® TL IM and Novozym^® 435 diminish by ca. 20 % after 9 reaction cycles.     

Production and Isolation of n‐Butyl Acrylate Using Pervaporation‐Aided Esterification Reaction: Kinetics and Optimization

Synthesis of n‐butyl acrylate by esterification of acrylic acid with n‐butyl alcohol was carried out in a batch membrane reactor. Optimization and design of the experiment was accomplished by response surface methodology with Box‐Behnken experimental design. The effects of different parameters like reaction temperature, catalyst concentration, molar ratio of alcohol to acid, and ratio of membrane surface to initial volume on water flux and conversion of acrylic acid were evaluated. A kinetic model for the esterification‐coupled pervaporation process was developed. Kinetic parameters were estimated by a nonlinear optimization technique in the MATLAB optimization toolbox. The experimental and simulation results were applied for developing a concept to effectively conduct a pilot‐scale esterification‐pervaporation experiment.     

Lipase‐catalysed synthesis of natural ethanol esters: effect of water removal on enzyme reutilisation

Lipase‐catalysed synthesis of ethanol esters using natural substrates is presented. Initial substrate concentrations, optimised through an experimental design, were 0.8 mol dm⁻³ lauric acid and 0.58 mol dm⁻³ ethanol, with an initial esterification rate (r₀) of 17.13 mmol dm⁻³ min⁻¹. Two different water removal systems were compared: a cooling exchanger in the reactor headspace and a vacuum‐based system. The best results were obtained with the second system. After six consecutive operations with the same enzyme, no loss of activity was observed. The yields obtained in all the runs were greater than 90%. Using the same approach three different natural esters (ethyl laureate, ethyl myristate and ethyl palmitate) were synthesised at 0.9 dm³ scale. Similar results were obtained in all three cases, with chemical yields always being greater than 90%. © 2000 Society of Chemical Industry     

Conductive‐diamond electrochemical advanced oxidation of naproxen in aqueous solution: optimizing the process

BACKGROUND: Electrochemical advanced oxidation treatment using boron‐doped diamond (BDD) electrodes is a promising technology to treat small amounts of toxic and biorefractory pollutants in water. This process has been tested on the degradation of naproxen, a common pollutant drug present in surface waters. To optimize the process a series of experiments have been designed to study the interaction between four variables: pH (over the range 5–11); current (0–320 mA cm^?2); supporting Na₂SO₄ electrolyte concentration (0–0.375 mol L^?1); and solution flow rate (Q_v) between 3.64 and 10.8 cm³ min^?1. RESULTS: Among these variables the influence of current was the greatest, the second was the salt concentration, the third flow rate, and the fourth pH. An ANOVA test reported significance for seven of the fourteen variables involved and the degradation of naproxen was optimized using response surface methodology. CONCLUSIONS: Optimum conditions for naproxen removal (100%) were found to be pH = 10.70, Q_v = 4.10 cm³ min^?1, current density = 194 mA cm^?2 using a supporting electrolyte concentration of 0.392 mol L^?1. Copyright © 2010 Society of Chemical Industry     

Study on preparation and properties of PVA‐SA‐PHB‐AC composite carrier for microorganism immobilization

Polyvinyl alcohol(PVA) bead crosslinked with boric acid has been widely utilized as a microorganism immobilization carrier. However, it has some disadvantages such as drastic cell viability loss, small adsorption capacity and mass transfer limitation. To improve upon these drawbacks, a new method to prepare PVA composite pieces with the addition of activated carbon (AC) and poly‐3‐hydroxybutyrate(PHB) was explored through a combination of freezing/thawing and the boric acid method and by using Tween‐80 to improve the mass transfer performance of hydrophobic organics. m‐Cresol and pyrene were used as representative compounds with benzene ring structures to model hydrophilic and hydrophobic organics in order to test the performance of PVA pieces. The results showed that, compared with the boric acid method alone, a combination of freezing/thawing and the boric acid method led to a decrease in total organic carbon(TOC) loss from 0.315 g g^?1 to 0.033 g g^?1 and increased the oxygen uptake rate(OUR) of microorganisms from 0.03 mg L^?1·min^?1 to 0.22 mg L^?1 min^?1. The m‐cresol equilibrium adsorption amount of the PVA‐SA(sodium alginate)‐PHB‐AC piece was 2.80 times that of the PVA‐SA piece. The diffusion coefficient of pyrene in the PVA‐SA‐PHB‐AC piece increased from 0.53×10^?9 m² min^?1 to 2.30×10^?9 m² min^?1 with increasing concentrations of Tween‐80 from 1000 mg L^?1 to 5000 mg L^?1. The PVA‐SA‐PHB‐AC composite carrier demonstrated great scope for immobilizing microorganisms for practical wastewater bio‐treatment. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39837.     

Lipase‐catalyzed esterification of cinnamic acid and oleyl alcohol in organic solvent media

The esterification of cinnamic acid (CA) and oleyl alcohol (OA) in organic solvent media by immobilized lipase Novozym 435 was optimized in terms of selected parameters, including the logarithm of the 1‐octanol/water partition coefficient of the organic solvent (log P, 0.29–4.5), initial water activity (a_w, 0.05–0.75), agitation speed (0–200 rpm), temperature (35–65 °C) and ratio of substrates (CA/OA, 1.0:0.5–1.0:6.0). The results showed that the more hydrophobic solvent mixtures and lower initial a_w values resulted in a higher enzymatic activity and bioconversion yield. The most appropriate solvent medium and initial a_w value was the mixture of iso‐octane/2‐butanone (85:15, v/v) and 0.05, respectively. The results also showed that an agitation speed of 150 rpm and a reaction temperature of 55 °C were optimal for the reaction system. The activation energy (E_a) of the esterification reaction was calculated as 43.6 kJ mol^?1. The optimal ratio of CA to OA was 1.0:6.0, with the absence of any inhibition by OA. Using the optimized conditions, the maximum enzymatic activity was 390.3 nmol g^?1 min^?1, with a bioconversion yield of 100% after 12 days of reaction. In addition, the electrospray ionization‐mass spectroscopy analysis confirmed that the major end product of the esterification reaction was oleyl cinnamate. Copyright © 2005 Society of Chemical Industry     

Kinetic study of the nonthermal effect of the esterification of octenyl succinic anhydride modified starch treated by microwave radiation

With cassava starch as a raw material and octenyl succinic anhydride as an esterifying agent, octenyl succinic anhydride modified starch (OSA–starch) was prepared in an aqueous medium and treated by water‐bath heating and microwave radiation at a certain temperature, respectively. The reaction kinetics of esterification were studied. The structural analysis and synthesis mechanism of OSA–starch were investigated by means of scanning electron microscopy and Fourier transform infrared spectroscopy. The differences in the esterification reaction kinetics between starches treated with water‐bath heating and microwave radiation were observed. Under the condition of water‐bath heating, the apparent activation energy of the esterification reaction was 52.22 ± 1.21 kJ/mol, and the pre‐exponential factor was 9018.20/min^?1. Under the condition of microwave radiation, the apparent activation energy of the esterification reaction was 50.13 ± 1.16 kJ/mol, and the pre‐exponential factor was 4510.21/min^?1. We found that microwave radiation could reduce both the activation energy of the reaction and the pre‐exponential factor. The lowering effect of the apparent activation energy was greater than that of the pre‐exponential factor under the condition of microwave radiation, and this resulted in increased reaction rates. The change in the esterification reaction kinetics was a nonthermal effect of microwave radiation on the esterification of cassava starch. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43909.     

Application of Taguchi Method in the Enzymatic Modification of Menhaden Oil to Incorporate Capric Acid

Structured lipids (SL) were produced using menhaden oil and capric acid or ethyl caprate as the substrate. Enzymatic reaction conditions were optimized using the Taguchi method L9 orthogonal array with three substrate molar ratio levels of capric acid or ethyl caprate to menhaden oil (1:1, 2:1, and 3:1), three enzyme load levels (5, 10, and 15% [w/w]), three temperature levels (40, 50, and 60 °C), and three reaction times (12, 24, 36 hours). Recombinant lipase from Candida antarctica, Lipozyme^® 435, and sn‐1,3 specific Rhizomucor miehei lipase, Lipozyme^® RM IM (Novozymes North America, Inc., Franklinton, NC, USA), were used as biocatalysts in both acidolysis and interesterification reactions. Total and sn‐2 fatty acid compositions, triacylglycerol (TAG) molecular species, thermal behavior, and oxidative stability were compared. Optimal conditions for all reactions were 3:1 substrate molar ratio, 10% [w/w] enzyme load, 60 °C, and 16 hours reaction time. Reactions with ethyl caprate incorporated significantly more C10:0, at 30.76 ± 1.15 and 28.63 ± 2.37 mol% versus 19.50 ± 1.06 and 9.81 ± 1.51 mol%, respectively, for both Lipozyme^® 435 and Lipozyme^® RM IM, respectively. Reactions with ethyl caprate as substrate and Lipozyme^® 435 as biocatalyst produced more of the desired medium‐long‐medium (MLM)‐type TAGs with polyunsaturated fatty acids (PUFA) at sn‐2 and C10:0 at sn‐1,3 positions.     

Noncatalytic Hydrolysis of Iminodiacetonitrile in Near‐Critical Water – A Green Process for the Manufacture of Iminodiacetic Acid

The hydrolysis of iminodiacetonitrile (IDAN) in near‐critical water, without added catalysts, has been successfully conducted with temperature and residence time ranges of 200–260 °C and 10–60 min, respectively. The effects of temperature, pressure, and initial reactant/water ratio on the reaction rate and yield have been investigated. The final reaction products primarily included iminodiacetic acid (IDA) and ammonia associated with other by‐products; gas formation was negligible. The maximum yield of IDA was 92.3 mol.‐% at 210 °C and 10 MPa, with a conversion of almost 100 %.The apparent activation energy and ln A of IDAN hydrolysis were evaluated as 45.77 ± 5.26 kJ/mol and 8.6 ± 0.1 min^–1, respectively, based on the assumption of first‐order reaction. The reaction mechanism and scheme were similar to those of base‐catalyzed reactions of nitriles examined in less severe conditions.