- Effect of polyvinylpyrrolidone on mesoporous silica morphology and esterification of lauric acid with 1-butanol catalyzed by immobilized enzyme
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Mesoporous silica materials with a range of morphology evolution, i.e., from curved rod-shaped mesoporous silica to straight rod-shaped mesoporous silica, were successfully prepared using polyvinylpyrrolidone (PVP) and triblock copolymer as dual template. The effects of PVP molecular weight and concentration on mesoporous silica structure parameters were studied. Results showed that surface area and pore volume continuously decreased with increased PVP molecular weight. Mesoporous silica prepared with PVP K30 also possessed larger pore diameter, interplanar spacing (d100), and cell parameter (a0) than that prepared with PVP K15 and PVP K90. In addition, with increased PVP concentration, d100 and a0 continuously decreased. The mechanism of morphology evolution caused by the change in PVP concentration was investigated. The conversion rate of lauric acid with 1-butanol catalyzed by immobilized Porcine pancreatic lipase (PPL) was also evaluated. Results showed that PPL immobilized on amino-functionalized straight rod-shaped mesoporous silica maintained 50% of its esterification conversion rate even after five cycles of use with a maximum conversion rate was about 90.15%.
- Zhang, Jinyu,Zhou, Guowei,Jiang, Bin,Zhao, Minnan,Zhang, Yan
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- Solvent-free biocatalytic interesterification of acrylate derivatives
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The ability of diverse commercial lipases and whole cells (fungal resting cells) to synthesise allyl and dichloropropyl acrylate from allyl dodecanoate through an interesterification process is presented. The process was carried out without solvent in a conventional batch system. The best biocatalyst among those studied was the commercial enzyme CALB (Candida antarctica lipase B immobilised onto a macroporous acrylic resin). The reaction was sensitive to water activity, and a decrease in the yield was observed at the highest activity studied. CALB could also be applied to diverse acrylic derivatives, although the yields decreased using either ethyl methacrylate or acrylic acid.
- Yara-Varón, Edinson,Eras Joli, Jordi,Torres, Mercè,Sala, Nuria,Villorbina, Gemma,Méndez, Jonh Jairo,Canela-Garayoa, Ramon
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- Effect of Ionic Liquids on the Chemical Equilibrium of Esterification of Carboxylic Acids with Alcohols
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The esterification of carboxylic acids with alcohols catalyzed by paratoluene sulfonic acid (pTSA) was studied in different room temperature ionic liquids. The chemical equilibrium of esterification can be tuned by using ionic liquids as solvents.
- Jiang, Tao,Chang, Yanhong,Zhao, Guoying,Han, Buxing,Yang, Guanying
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- Performance in synthetic applications of a yeast surface display-based biocatalyst
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This work demonstrates the effectiveness of yeast surface display (YSD) as a scaffold for biocatalysts in hydrophobic, non-aqueous environments. Two lipases, Candida antarctica lipase B (CalB) and Photobacterium lipolyticum sp. M37 lipase (M37L), were immobilized independently by surface display on Saccharomyces cerevisiae. The two YSD biocatalysts were employed to synthesize esters of butanol and saturated fatty acids of varying length (8 to 16 carbons) in heptane. Effects of fatty acid chain length and temperature on the esterification reaction were examined. The YSD catalysts synthesized butyl decanoate in 10 repeated batches with little loss in activity. Compared to a commercial immobilized lipase (Novozym 435), the activity of both YSD lipases was lower on a mass loading basis, but higher when normalized on estimates of protein loading. Initial-rate kinetics of the butyl decanoate reaction were measured for the CalB-displaying yeast. Kinetics and apparent activity of M37L in the multi-batch experiments depend heavily on water concentration; kinetics for M37L could not be elucidated with initial-rate methods. The difference between CalB and M37L in water requirements illustrates a critical parameter for optimization of lipase activity in non-aqueous environments. The activity of both lipases in a completely hydrophobic environment is a step towards more economical biocatalysis of industrial esterification.
- Eby,Peretti
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- An improved greener esterification of fatty alcohols using a renewable acid-ionic liquid couple as catalyst-solvent
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We have developed a simple and efficient method for the esterification of various organic acids with C4-C18 alcohols using the 1-octyl-3-methyl- imidazolium tetrafluoroborate-para-toluenesulphonic acid (OMIM/BF 4-PTSA) couple, without organic solvent, either by classic heating or by microwave irradiation. The utilisation of the OMIM/BF4-PTSA couple presents considerable advantages: high yield, low temperature, short reaction time, isolation of the ester by simple decantation, easy reuse of the catalyst couple.
- Nguyen, Hoang-Phuong,Znifeche, Samira,Baboulene, Michel
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- A novel poly(p-styrenesulfonic acid) grafted carbon nanotube/graphene oxide architecture with enhanced catalytic performance for the synthesis of benzoate esters and fatty acid alkyl esters
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Considering the issue of low yield in the synthesis of benzoate esters and fatty acid alkyl esters, designing a high catalytic activity composite catalyst is very significant and attractive. In this study, the rational design strategy was used to develop a novel poly(p-styrenesulfonate acid, namely PSSF) grafted multi-walled carbon nanotube composite with graphene oxide nanomaterial (PSSF-mCNTs-GO) using a simple two-step method. FT-IR and Raman spectroscopy, XRD, SEM, TEM, and NH3-TPD were used to characterize the inorganic-organic hybrid material. In particular, the addition of GO remarkably enhanced its catalytic performance in the production of fatty acid alkyl esters (92.16%) and benzoate esters (90.27%), in which the conversion was more than doubled as a result of its strong π-π interaction with the substrate. In addition, PSSF-mCNTs-GO can be separated from the substrate conveniently and still maintained a relatively high catalytic activity even after 6 times recycling, which indicates its rather good reusability. This novel catalyst is promising in the synthesis of biodiesel and benzoate esters.
- Bian, Gang,Jiang, Pingping,Zhang, Weijie,Jiang, Kelei,Hu, Ling,Jian, Zhang,Shen, Yirui,Zhang, Pingbo
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- Evaluation of deep eutectic solvents as new media for Candida antarctica B lipase catalyzed reactions
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This study aimed at analyzing the advantages and limitations of several deep eutectic solvents (DESs) as 'green solvents' for biotransformation using immobilized Candida antarctica lipase B as catalyst. The transesterification of vinyl laurate was chosen
- Durand,Lecomte,Baréa,Piombo,Dubreucq,Villeneuve
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- Novel SO3H-functionalized polyoxometalate-based ionic liquids as highly efficient catalysts for esterification reaction
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Three novel heteropolyanion-based Br?nsted acidic ionic liquids (BAILs), butane mono sulfoacid-functionalized 1,10-phenanthrolinum, butane mono and bis sulfoacid-functionalized 1,4-dimethylpiperazinium salts of phosphortungstate catalyst (PhBs1-PW, [PipBs1]3-PW and [PipBs2]3-(PW)2) were synthesized and well characterized with FTIR, 1H and 13C NMR, Electro-Spray Ionization Mass Spectrometry (ESI-MS), Elemental analysis (CHNS), EDX and TG analysis techniques. The esterification reactions of monocarboxylic acids with monohydric alcohols were carried out using these catalysts. The introduced catalysts present a self-separation performance after reaction, which can be easily recovered and quite steadily reused as confirmed by six-run recycling test. Moreover, bis sulfoacid-functionalized 1,4-dimethylpiperazinium salt of phosphortungstate showed the best catalytic performance among the prepared catalysts for the esterification reaction.
- Keshavarz, Mosadegh,Iravani, Nasir,Parhami, Abolfath
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- A novel Bronsted acidic heteropolyanion-based polymeric hybrid catalyst for esterification
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A new SO3H-functionalized HPA-based acidic polymeric hybrid was prepared by coupling task-specifically designed SO3H-functionalized polymeric ionic liquid with Keggin-structured heteropolyanion, and characterized by 1H NMR, FT-IR, TG, XRD, BET, Hammett indicator, melting point, and elemental analysis. Its catalytic performance for esterification of alcohols with carboxylic acids was studied under solvent-free conditions. The results demonstrate that the polymeric hybrid is a highly active and selective solid catalyst for various esterifications, and can be easily recovered and steadily reused.
- Leng, Yan,Jiang, Pingping,Wang, Jun
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- Robust acidic pseudo-ionic liquid catalyst with self-separation ability for esterification and acetalization
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The novel acidic pseudo-ionic liquid catalyst with self-separation ability has been synthesized through the quaternization of triphenylphosphine and the acidification with silicotungstic acid. The pseudo-IL showed high activities for the esterification with average conversions over 90%. The pseudo-IL showed even higher activities for acetalization than traditional sulfuric acid. The homogeneous catalytic process benefited the mass transfer efficiency. The pseudo-IL separated from the reaction mixture automatically after reactions, which was superior to other IL catalysts. The high catalytic activities, easy reusability and high stability were the key properties of the novel catalyst, which hold great potential for green chemical processes.
- Shi, Yingxia,Liang, Xuezheng
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- Tunable aryl imidazolium ionic liquids (TAIILs) as environmentally benign catalysts for the esterification of fatty acids to biodiesel fuel
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Herein, we describe the synthesis of tunable aryl imidazolium ionic liquid catalysts and tested for esterification of fatty acids to biodiesel. In this work, six tunable aryl imidazolium ionic liquids (TAIILs) 1a-1f were prepared. These ionic liquids were used as the economical and reusable catalysts for the synthesis of biodiesel fuels. The reaction has been preceded in a monophase at 80 °C for 4 h, after which the product was separated from the catalyst system by a simple liquid/liquid phase separation at room temperature with excellent yields. With the simple post-process, the catalyst is reusable at least 6 times. This novel method offers a short reaction time, good yields, and environmentally benign characteristics.
- Ho, Wen-Yueh,Lin, Wesley,Lin, Yi-Jyun,Luo, Shun-Yuan,Pantawane, Amit,Su, Po-Fang,Thul, Mayur,Tseng, Shao-An,Wu, Hsin-Ru
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- Sulfonic acid modified hollow polymer nanospheres with tunable wall-thickness for improving biodiesel synthesis efficiency
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Precisely designing the morphology and size of nanostructures is vital in green chemistry as various advanced applications depend upon the shapes and dimensions of the functionalised materials. Herein, we report on a green and efficient self-assembly strategy for synthesising hollow polymeric nanospheres with tunable wall thicknesses. The morphology and shell thickness of the nanospheres can be easily tailored by rationally manipulating monomer and catalyst combinations during the one-pot Friedel-Crafts polymerisation process, without using any templates or surfactants. Heterogeneous solid sulfonic acid catalysts can be easily achievedviathe post-sulfonation strategy. These porous materials have preferable surface areas, ordered hollow pore structures, and accessible acidic sites, and they serve as promising catalysts for biodiesel production. This study provides insights into the production of template- and metal-free based catalysts for biofuel production, which is imperative for the green and efficient design and manufacture of high-activity heterogeneous catalysts.
- Kim, Il,Kim, Ji Su,Song, Wenliang,Varyambath, Anuraj,Zhang, Yu
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p. 3572 - 3583
(2020/08/28)
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- Development and Validation of a Novel Free Fatty Acid Butyl Ester Gas Chromatography Method for the Determination of Free Fatty Acids in Dairy Products
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Accurate quantification of free fatty acids in dairy products is important for both product quality control and legislative purposes. In this study, a novel fatty acid butyl ester method was developed, where extracted free fatty acids are converted to butyl esters prior to gas chromatography with flame ionization detection. The method was comprehensively validated to establish linearity (20-700 mg/L; R2 > 0.9964), limits of detection (5-8 mg/L), limits of quantification (15-20 mg/L), accuracy (1.6-5.4% relative error), interday precision (4.4-5.3% relative standard deviation), and intraday precision (0.9-5.6% relative standard deviation) for each individual free fatty acid. A total of 17 dairy samples were analyzed, covering diverse sample matrices, fat content, and degrees of lipolysis. The method was compared to direct on-column injection and fatty acid methyl ester methods and overcomes limitations associated with these methods, such as either column-phase absorption or deterioration, accurate quantification of short-chain free fatty acids, and underestimation of polyunsaturated free fatty acid.
- Mannion, David T.,Furey, Ambrose,Kilcawley, Kieran N.
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p. 499 - 506
(2019/01/08)
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- A novel application of terminal alkynes as the homogeneous catalysts for acetalization and esterification
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The theoretical study focused on the possible use of low-molecular-weight mono-as well as multifunctional terminal alkynes as catalysts for two reactions, which are known to be typically acid catalyzed - acetalization and esterification, is presented in this study. Multifunctional terminal alkynes [(diethynylbenzenes, triethynylbenzene, and tetrakis(4-ethynylphenyl)methane]were significantly more active than the monofunctional ones (cyclopropylacetylene, phenylacetylene, 3-cyclohexylprop-1-yne, 1-ethynyl-2-fluorobenzene, 1-ethynyl-4-fluorobenzene, 4-ethynyltoluene, 4-tert-butylphenylacetylene, and 2-ethynyl-α,α,α-trifluorotoluene), this fact can be partly explained by the higher amount of ethynyl groups per alkyne molecule. We confirmed that terminal ethynyl groups in low-molecular-weight alkynes can successfully act as acid catalytic centers for acetalization as well as for esterification.
- Sekerová, Lada,Vysko?ilová, Eli?ka,?erveny, Libor,Sedlá?ek, Jan
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p. 2877 - 2882
(2019/04/17)
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- Immobilization of lipase on biocompatible co-polymer of polyvinyl alcohol and chitosan for synthesis of laurate compounds in supercritical carbon dioxide using response surface methodology
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Biocompatible co-polymer matrix has great importance for enzyme immobilization and subsequent biocatalytic applications to synthesize important organic moieties. Citronellyl laurate is a fatty-acid-ester having pleasant fruity aroma and widely used as/in emulsifier, lubricant in textile, paint or ink-additives, surfactants, perfumery and food-flavouring ingredient. In present study, Burkholderia cepacia lipase (BCL) was immobilized on biodegradable co-polymer of chitosan (CHI) and polyvinyl alcohol (PVA). The synthesized bio-catalyst {PVA:CHI:BCL (6:4:2.5)} was characterized by SEM, TGA, lipase assay and protein-content analysis. This biocatalyst was applied to synthesize citronellyl laurate in supercritical carbon-dioxide (SC-CO2) using response surface methodology with five-factor-three-level Box-Behnken-design to optimize reaction parameters (citronellol: 8.5 mmol; vinyl laurate: 19.87 mmol; biocatalyst: 175.6 mg; temperature: 46.02 °C; pressure: 8.81 MPa) which provided 94 ± 1.52% yield. The protocol is extended to synthesize various important 12 laurate compounds with excellent yield (90-98%) and noteworthy recyclability (upto studied 5 recycles). Interestingly, immobilized PVA/CHI/lipase biocatalyst showed 4-fold higher bio-catalytic activity than free lipase in SC-CO2. Moreover, the biocatalyst activity assessment study showed remarkable activity-stability of immobilized biocatalyst in SC-CO2 media as compared to free enzyme. Thus, present protocol demonstrated potential biocatalytic applications for synthesis of important laurate compounds with excellent recyclability in SC-CO2 as greener biocatalyst and reaction medium.
- Badgujar, Kirtikumar C.,Bhanage, Bhalchandra M.
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p. 1224 - 1236
(2015/07/08)
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- Esterification of free fatty acids (Biodiesel) using nano sulfated-titania as catalyst in solvent-free conditions
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Nano sulfated titania was tested as catalyst for esterification of free fatty acids, specially methanolic and ethanolic esterification of stearic acid (biodiesels). Factorial design evidenced a positive effect of reaction temperature, amount of catalyst, and solvents on ester conversion. This nano-sized sulfated titania has been prepared by a sol-gel hydrothermal process. This prepared sulfated titania showed high catalytic activity in direct esterification of fatty acids as well as benzoic acids with various alcohols and phenols under solvent-free conditions. This method is of great value because of its environmentally benign character, easy handling, high yields, convenient operation, and green. FT-IR studies are shown that the catalyst can be reused for acylation without loss of catalytic activity.
- Hosseini-Sarvari, Mona,Sodagar, Esmat
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p. 229 - 238
(2013/05/09)
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- TRANSESTERIFICATION PROCESS USING MIXED SALT ACETYLACETONATES CATALYSTS
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This invention is directed to a general catalyst of high activity and selectivity for the production of a variety of esters, particularly acrylate and methacrylate-based esters, by a transesterification reaction. This objective is achieved by reaction of an ester of a carboxylic or a carbonic acid, in particular of a saturated or unsaturated, typically, a 3 to 4 carbon atom carboxylic acid; with an alcohol in the presence of a catalyst comprising the combination of a metal 1,3-dicarbonyl complex (pref. Zn or Fe acetylacetonate) and a salt, in particular an inorganic salt, pref. ZnCl2, LiCI, NaCI, NH4CI or Lil. These catalysts are prepared from readily available starting materials within the reaction medium without the need for isolation (in-situ preparation).
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Paragraph 0074; 0075
(2013/04/13)
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- Novel Br?nsted acidic deep eutectic solvent as reaction media for esterification of carboxylic acid with alcohols
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New halogen-free Br?nsted acidic deep eutectic solvents (DES) have been prepared by mixing new quaternary ammonium methanesulfonate salts with p-toluenesulfonic acid (PTSA). They have been used as dual solvent-catalyst for esterification of several carboxylic acids with different alcohols with a reagent molar ratio of 1:1. The method is mild, safe, and simple. Ease of recovery and reusability of DES with high activity makes this method efficient and eco-friendly. The tunability of DES properties, attained by changes in the cation, was performed in order to achieve various esters in good yields.
- De Santi, Valerio,Cardellini, Fabio,Brinchi, Lucia,Germani, Raimondo
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scheme or table
p. 5151 - 5155
(2012/09/25)
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- Specific enzyme-catalyzed hydrolysis and synthesis in aqueous and organic medium using biocatalysts with lipase activity from Aspergillus niger MYA 135
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In the present study, the specific hydrolytic activity of three biocatalysts such as the constitutive mycelium-bound lipase, the induced mycelium-bound lipase and the lyophilized induced supernatant from A. niger MYA 135 was evaluated in both aqueous and organic media.A direct correlation between activity in water and n-hexane was not observed for the same hydrolytic reaction. The n-hexane/water activity ratio (RO/A) was applied to characterize the activity in organic medium. The three biocatalysts showed RO/A values higher than 1 for hydrolysis of long-chain fatty acid esters, demonstrating a higher specific hydrolytic activity in organic solvent than in water. A different behavior was observed during hydrolysis of middle-chain fatty acid esters, which was higher in aqueous medium (R O/Adw) observed in a reaction mixture containing propanol and p-nitrophenyl laurate. Finally, both p-nitrophenyl caprate (C10) and p-nitrophenyl laurate (C12) were preferentially methanolized by the lyophilized induced supernatant, being this lipase activity the most specific biocatalyst preparation under transesterification conditions. A selectivity-based analysis of each lipase preparation toward transesterification or hydrolysis in organic medium was evaluated as well. Springer Science+Business Media, LLC 2012.
- Romero, Cintia M.,Pera, Licia M.,Loto, Flavia,Baigori, Mario D.
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p. 1361 - 1368
(2013/01/15)
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- Dodecanoic acid derivatives: Synthesis, antimicrobial evaluation and development of one-target and multi-target QSAR models
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In this study a series of dodecanoic acid derivatives (1-30) were synthesized and evaluated for in vitro antimicrobial activity against the panel of Gram positive, Gram negative bacterial and fungal strains. 4-Nitro phenyl dodecanoate (4) and quinolin-8-yl dodecanoate (5) emerged as most effective antibacterial agents, and 1-(4-benzylpiperazin- 1-yl) dodecan-1-one (15) was found to be the most effective antifungal agent amongst the synthesized dodecanoic acid derivatives. Quantitative structure activity relationship (QSAR) studies performed by the development of one-target and multi-target models indicated that multitarget model was effective in describing the antimicrobial activity of dodecanoic acid derivatives as well demonstrated the importance of topological parameter, zero-order molecular connectivity index (0X). Springer Science+Business Media, LLC 2010.
- Sarova, Devinder,Kapoor, Archana,Narang, Rakesh,Judge, Vikramjeet,Narasimhan, Balasubramanian
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experimental part
p. 769 - 781
(2012/05/20)
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- PRODUCTION OF DETERGENT RANGE ALCOHOLS
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This invention relates to a process for the production of a mixture of detergent-range alcohols having an average of between 8 and 20 carbon atoms per molecule. The process includes the steps of providing a hydrocarbon stream containing olefins and paraffins in which more than 5% by volume of olefin molecules in the hydrocarbon stream have a total number of carbon atoms which is different from the total number of carbon atoms of the most abundant two carbon numbers of olefins in the hydrocarbon stream; reacting the hydrocarbon stream with CO and an alcohol in the presence of a catalyst in a hydroesterification reaction to form a hydrocarbon stream containing esters and paraffins; separating esters from the hydrocarbon stream containing esters and paraffins; and subjecting the esters to a hydrogenation reaction to provide the mixed alcohol product.
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Page/Page column 3
(2009/01/24)
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- Heteropolyanion-based ionic liquids: Reaction-induced self-separation catalysts for esterification
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(Figure Presented) It comes out in the wash: In the esterification of citric acid with n-butanol, heteropolyanion-based ionic liquid (IL) catalysts show high catalytic activity, self-separation, and easy reuse. The good solubility in reactants, nonmiscibility with ester product, and high melting point of the IL catalysts enable the reaction-induced switching from homogeneous (b in the picture) to heterogeneous (c) with subsequent precipitation of the catalyst (d).
- Leng, Yan,Wang, Jun,Zhu, Dunru,Ren, Xiaoqian,Ge, Hanqing,Shen, Lei
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experimental part
p. 168 - 171
(2009/04/18)
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- Process for preparation of an ester using a polyaniline salt as catalyst
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The invention relates to a process for preparation of an ester using a polyaniline salt as catalyst.
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- Fat Hydrolysis and Esterification by a Lipase from Humicola lanuginosa
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The hydrolysis and esterification by a thermostable lipase from Humicola lanuginosa No. 3 were investigated.Both reactions occurred readily at temperatures between 45-50 deg C.Esterification by the enzyme with glycerol was observed to be specific towards fatty acids with carbon numbers of C12-C18.Lauric acid esters with different alcohols such as primary alcohols, terpene alcohols, etc., were also synthesized readily.Esterification by the enzyme was adversely affected by the water content (optimum, ca. 7percent), however, the hydrolysis rate increased rapidly with increasing water content (optimum, ca. 60percent).The enzyme showed increased activity in organic solvent-aqueous reaction systems.Nevertheless, hydrolysis in complete organic phase reactions was found not to be feasible.Hydrolysis at a higher temperature (50 or 55 deg C) in a solvent free phase was almost the same as that in organic solvent-aqueous phase reactions.The components of glycerides varied considerably during hydrolysis, whereby esterification resulted in a higher quantity of mono- and diglycerides (about 40percent), compared to in the case of hydrolysis, for which the value was about 10-20percent.
- Omar, Ibrahim Che,Nishio, Naomichi,Nagai, Shiro
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p. 2153 - 2160
(2007/10/02)
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