Enzymatic production of 1-butyl oleate ester using Rhizopus oryza cell system

Number of pages: 147 File Format: word File Code: 31819
Year: 2013 University Degree: Master's degree Category: Chemical - Petrochemical Engineering
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  • Summary of Enzymatic production of 1-butyl oleate ester using Rhizopus oryza cell system

    Master thesis

    Chemical-Biotechnology Engineering

    Abstract

    Lipase is a carboxylic ester hydrolase enzyme that acts on triacylglycerol to release fatty acids, glycerides and glycerol. The discovery of the ability of lipase to catalyze the esterification reaction started a broad chapter in the field of this enzyme's functions. In this study, knowing the ability to produce lipase enzyme attached to the cell membrane by Rhizopus oryza, the growth curve of the microorganism was drawn to determine the duration of logarithmic growth and determine the optimal production time of lipase enzyme. synthetic and hydrolytic activity for two growth forms; Immersed and stabilized on the basis of loofah cellulose, it was calculated according to the duration of growth. The membrane-bound enzyme activity produced by the stabilized species will reach its maximum during the culture period. The stabilized cells were used for the catalysis of the synthesis reaction of 1-butyl oleate ester in a closed system, in the presence and absence of hexane solvent.  The system containing hexane was chosen to improve the mass transfer and kinetic parameters and the efficiency of 86% and to continue the studies. Then, the effective parameters on the ester synthesis reaction in the presence of normal hexane solvent were optimized to achieve the maximum efficiency in the shortest time. The equilibrium reaction of the synthesis of 1-butyl oleate ester at 37°C and 250 rpm in the presence of normal solvent hexane and 1.5 g of molecular sieve, in the molar ratio of 1:1 reactants with a concentration of 0.3 M, reached a high efficiency of 95%. Also, with the use of biocatalyst for 20 consecutive periods, a decrease in efficiency of less than 10% was observed. Oleate-optimization of reaction conditions

    1          Introduction

    Today, one of the biggest human challenges is climate change and environmental pollution caused by industrial activities. Releasing dangerous chemicals and heavy metals caused by the effluents of chemical factories causes changes in the ecosystem.

    Green chemistry[1] as well as sustainable development[2] suggests theories that tend to reduce or completely eliminate the production of dangerous and toxic products, resulting in less waste production and optimal energy consumption.

    Using Modern tools, including biotechnology, in order to expand environmentally friendly processes and produce biochemical products, is one of the solutions for green chemistry and sustainable development.

    The use of biocatalysts including enzymes or the whole cell (as an enzyme source or enzyme production system) to achieve economic and environmentally friendly processes is completely in harmony with the laws of green chemistry to reduce environmental pollution.

          The history of the use of enzymatic processes can be traced back to ancient civilizations. Today, nearly 4,000 enzymes are known, and of these, about 200 have been produced on a commercial scale. Most industrial enzymes are of microbial origin. By the 1960s, total annual revenue from enzyme sales was several million dollars, and with advances in biochemical production science, fermentation processes, and recovery methods, large numbers of these enzymes have been produced cost-effectively. Therefore, a significant growth was observed in the commercial enzyme market[1].

    The expansion of enzyme technology is an important success in the biotechnology industry. According to the statistics of Novazaim Company [3], "this company has a 47% share in the sale of industrial enzymes worldwide in consecutive years, and in 2012, with a growth of 7% compared to the previous year, it reported annual sales, approximately equivalent to 1.984 billion US dollars" [2], this indicates the increasing importance and use of enzyme products at the global level. A major share of the industrial enzyme market belongs to hydrolytic enzymes [4] such as proteases, amylases, amidases, esterases and lipases.) due to its multifaceted properties that have wide applications in various industries, including in the detergent, food and flavoring, pharmaceutical, cosmetic and health industries, the production of esters and amino acid derivatives, the production of agricultural chemicals and biopolymers, the production of valuable chemical oil products, the separation of racemic mixtures, diagnostic tools and other medical applications, the leather, textile and paper industries, the treatment of wastewater and oil pollutants, the production of biofuels, biosensors, etc., as a key enzyme in Biotechnology industries are progressing rapidly.

    Lipase enzyme is a member of the class of hydrolases that act on the carboxylic ester bonds present in triglycerides in order to release free fatty acid and glycerol. The natural substrate of lipases are long-chain triglycerides, which have little solubility in water; Therefore, the reaction occurs at the interface of water and lipid. In the organic environment, in the presence of a small amount of water, lipases show a unique ability to catalyze the photo reaction (reactions of ester synthesis [5] and the transfer of organic groups from an alcohol, acid, amide or an ester to another ester [6]). Therefore, despite the high specific performance of this enzyme due to its chemically, spatially and spatially specific active site, it has a wide range of substrates[3]. Among animal, plant and micro-organism sources; lipase enzyme produced by microbial sources; Fungal and bacterial have shown a wide application in the fields of biotechnology and organic chemistry [4].

    Filamentous fungi have shown a very high potential to produce a variety of extracellular lipases. Extracellular enzymes are usually prepared and used in pure form. However, the practical application of these enzymes is limited to certain industries due to the economic limitations caused by the complexity of purification operations and their instability [5]. Therefore, intracellular lipases (attached to the cell membrane) are attracting more attention due to their more specific catalysis and greater selectivity than the extracellular type, as well as the lack of complex stages of enzyme recovery, purification and enzyme stabilization. have done [6].

    The simplicity of operation and cost reduction of dried fungal cells is the reason for their direct use in hydrolysis reactions and ester synthesis, which will be of special importance in industrial applications. However, due to the low specific activity, their use is still limited [7]. The low specific activity of the biomass can be attributed to the low amount of intracellular enzyme compared to the mass of the cell mass or the inactivation of this enzyme.

    In order to increase and improve the activity of the cell and the intracellular enzyme, many efforts have been made to increase the amount of enzyme production and reduce its secretion outside the cell and maintain its activity. According to the studies, the production and secretion of enzymes depends on factors such as time, temperature, shaker speed, pH, and the type and amount of cell culture substrate as well as cell growth morphology[8]. Biodiesel as a suitable alternative to fossil fuels by improving the economic, environmental and social problems of fossil fuels is one of the most important topics in recent studies. Among the disadvantages of biodiesel are: Its high viscosity compared to fossil fuels. New diesel engines with fuel injection systems are sensitive to changes in fuel viscosity, so reducing fuel viscosity is a suitable solution to solve this problem. Among commercially produced esters, 1-butyl-oleate is widely effective in the field of diesel fuel additives and causes fuel viscosity reduction. Also, among its other uses, we can mention the lubrication of polyvinyl chloride (PVC) [7], the agent resistant to water and other hydraulic fluids [9]. Disadvantages such as the use of acid catalysts and the need for costly upstream processes, long time, high temperature and low efficiency in the chemical method are significant, which will be overcome by using biotechnology processes that occur under biologically balanced conditions and with specific performance on the substrate.

  • Contents & References of Enzymatic production of 1-butyl oleate ester using Rhizopus oryza cell system

    List:

    The first chapter. 1

    1    Introduction. 2

    The second chapter. 7

    A review of the concepts and studies done. 7

    2    Preface. 8

    2.1 Enzyme. 8

    2.2 Enzyme history. 9

    2.3 Lipase enzyme 10

    2.4 The difference between lipase enzyme and carboxylesterase 11

    2.5 Reasons for increased attention of researchers to lipase enzyme 11

    2.6 Lipase enzyme reactions 12

    2.7 Characteristics of lipase enzyme 14

    2.7.1 Structural properties (presence Cap on the active site) 14

    2.7.2 Surface activation. 15

    2.7.3 Substrate selectivity 16

    2.7.4 Resistance to temperature increase and changes (pH) 19

    2.8 Lipase enzyme production 20

    2.8.1 Sources of lipase enzyme production 20

    2.8.2 Comparison of bacterial and fungal lipases and their applications 22

    2.8.3 Lipases of filamentous fungi. 23

    2.8.4 Isolation of enzymes 24

    2.8.5 Microorganism growth and enzyme induction. 26

    2.9 Cell stabilization. 27

    2.9.1 Comparing the advantages and disadvantages of enzyme and cell immobilization. 27

    2.9.2 Use of enzyme or fixed cell. 29

    2.9.3 cell stabilization methods. 30

    2.9.4 Selection of retainer and method for cell stabilization. 36

    2.9.5 The oozing mechanism and location of lipase in the cell of Rhizopus oryza and the effect of stabilization on its oozing. 42

    2.10 Lipase enzyme activity measurement methods 45

    2.10.1 Lipase enzyme dehydration activity measurement methods 45

    2.10.2 Lipase enzyme synthetic activity measurement methods 46

    2.11 Lipase enzyme applications 47

    2.12 Ester synthesis reactions. 49

    2.12.1 Parameters affecting the progress of ester synthesis reaction. 51

    2.12.2 Synthesis of 1-butyl oleate ester. 54

    The third chapter. 62

    Materials and methods 62

    3 Preface. 63

    3.1 Chemicals. 63

    3.2 Tools and devices used 64

    3.3 Microorganism. 65

    3.4 Description of experiments 66

    3.4.1 Solid culture of microorganism. 66

    3.4.2 Production of mushroom spore solution. 66

    3.4.3 Microorganism liquid culture. 68

    3.5 Preparation of cellular biocatalyst. 68

    3.5.1 Loofah sponge as a cell holder. 68

    3.5.2 Stabilization of Rhizopus oryza fungus and preparation of biocatalyst. 68

    3.5.3 Determining the amount of cellular biocatalyst water. 70

    3.6 Drawing the growth curve of the microorganism Rhizopus oryza in free form. 70

    3.7 Activation of molecular sieves. 71

    3.8 Turbidity measurement method of measuring free fatty acids. 71

    3.8.1 Preparation of copper acetate-pyridine reagent solution. 72

    3.8.2 Drawing the standard curve of free fatty acid absorption to measure esterification activity. 72

    3.9 Enzyme specific activity assay. 73

    3.9.1 Synthetic activity of enzyme system (cellular biocatalyst) - ester production. 74

    3.9.2 Dehydration activity of enzyme system (cellular biocatalyst) 75

    3.10 Synthesis reaction of 1-butyl oleate ester. 75

    3.10.1 Analysis to determine the progress of the reaction. 76

    3.10.2 Analysis of the manufactured product by gas chromatography-mass spectroscopy method. 76

    3.11 Selection of the reaction system for the synthesis of 1-butyl oleate ester in the presence and absence of solvent. 77

    3.11.1 Synthesis of 1-butyl oleate ester in the presence of hexane solvent. 77

    3.11.2 Synthesis of 1-butyl oleate ester in the absence of solvent. 78

    3.11.3 Comparison of the effect of mass transfer limitations inside the loofah piece, on the initial speed of the reaction in the presence of solvent and in the absence of solvent. 78

    3.12 Optimizing reaction conditions for 1-butyl oleate ester synthesis in the presence of hexane solvent. 81

    3.12.1 Investigating the effect of molar ratio of solvent to substrate on reaction efficiency and speed. 81

    3.12.2 Investigating the effect of increasing the concentration of the alcoholic substrate. 81

    3.12.3    Acidic substrate. 82

    3.12.4 Investigating the effect of catalyst concentration on the efficiency and initial speed of the reaction. 82

    3.12.1 Investigating the effect of removing water on reaction efficiency. 83

    3.12.2 Investigating changes in efficiency in the successive use of cellular biocatalyst. 83

    The fourth chapter. 84

    Results and analyzes 84

    4 Preface. 85

    4.1 Growth curve of Rhizopus oryza 85

    4.2 Investigation and comparison of cellular biocatalyst activity in free and stabilized form.86

    4.2.1 The hydrolytic activity of the enzyme system (cellular biocatalyst) 86

    4.2.2 The synthetic activity of the enzyme system (cellular biocatalyst) - ester production. 88

    4.3 Selection of the reaction system for the synthesis of 1-butyl oleate ester in the presence and absence of solvent. 89

    4.3.1 Synthesis of 1-butyl oleate ester in the presence of hexane solvent. 89

    4.3.2 Synthesis of 1-butyl oleate ester in the absence of solvent. 91

    4.3.3 Comparison of the internal mass transfer parameter of the loofah piece in the presence and absence of solvent. 92

    4.4 Optimizing reaction conditions for the synthesis of 1-butyl oleate ester in the presence of hexane solvent. 97

    4.4.1 Investigating the effect of molar ratio of solvent to substrate on reaction efficiency and speed. 97

    4.4.2 Investigating the effect of catalyst concentration on the efficiency and initial speed of the reaction. 99

    4.4.3 Investigating the effect of increasing the concentration of the alcoholic substrate. 100

    4.4.4 Investigating the effect of increasing the concentration of the acidic substrate. 101

    4.4.5 Investigating the effect of removing water on reaction efficiency. 103

    4.4.6 Investigating the yield changes in the successive use of cellular biocatalyst. 105

    Conclusion and suggestions. 107

    5 Preface. 108

    5.1 Conclusion. 108

    5.2 Suggestions for future studies. 111

    5.2.1 Biocatalyst. 111

    5.2.2 Reaction substrate. 112

    5.2.3 Reaction conditions. 112

    5.2.4 Product. 113

    Resources and references. 114

    Appendix. 114

     

    Source:

     

    1.Sharma, R.; Chisti, Y.; Chand, U. ; "Production, purification, characterization, and applications of lipases", Biotechnology Advance 19, 627-662, 2001

    2.      Novozymes; pagetitle: https://report2012.novozymes.com/Menu/The+Novozymes+Report+2012/Report/Company+profile

    3.Gupta,R.; Gupta, N.; Rathi, P.; "Bacterial lipases: an overview of production, purification and biochemical properties", Applied microbiology and biotechnology 64, 763-81, 2004

    4. Yahya, Ahmad R. M.; Anderson, William A.; Murray Moo-Young; "Ester synthesis in lipase catalyzed reactions", Enzyme and Microbial Technology 23, 438-450, 1998

    5. Hama, S.; Sriappareddy, T. ; Takahiro, F.; Kazunori, M.; Hideki, Y.; Akihiko, K.; Hideki, F.; "Lipase localization in Rhizopus oryzae cells immobilized within biomass support particles for use as whole-cell biocatalysts in biodiesel-fuel production", Journal of bioscience and bioengineering 101,328-333, 2006

    6.Salleh, A. B.; Musani, R.; Basri, M.; Ampon, M.; Yunus, W.M.Z.; Razak, C.N.A.; "Extra and intra-cellular lipases from a thermophilic Rhizopus oryzae and factors affecting their production", Can. J. Microbiol. 39, 1991-1994, 1993

    7. Chen, J.; Wang, J.; "Wax ester synthesis by lipase-catalyzed esterification with fungal cells immobilized on cellulose biomass support particles", Enzyme and Microbial Technology 20, 615-622, 1997

    8. Nakashima, T.; Fukuda, H.; Kyotani, S.;” Culture conditions for intracellular lipase production by Rhizopus chinensis and its immobilization within biomass support particles", Journal of Fermentation Technology 66, 441-448, 1988

    9.Baron, M.; Sarquiz, M. Inez M.; Baigori, M.; Mitchell, David, A.; kriger, N.;" A comparative study of the synthesis of n-butyl-oleate using a crude lipolytic extract of Penicillum coryophilum in water-restricted environments", Journal of Molecular Catalysis B: Enzymatic 34, 25-32, 2005

    10. Leon, R.; Fernandes, P.; Pinheiro H.K.; Cabral J.M.S.; "Whole-cell biocatalysis in organic media", Enzyme and Microbial Technology 23, 483-500, 1998

    11. Drauz, K., & Waldmann, H.; "Enzyme Catalysis in Organic Synthesis: A Comprehensive Handbook, 2 vols" Berlin: Wiley-VCH, 2002

    12. Gilham, D.; Lehner, R.;” Techniques to measure lipase and esterase activity in vitro", Methods (San Diego, Calif.) 36, 139-147, 2005

    13. Chahiniana, H.; Sarda, L.; "Distinction Between Esterases and Lipases: Comparative Biochemical Properties of Sequence-Related Carboxylesterases", Protein and Peptide Letter 16, Oct 2009

    14.Bornscheuer, T.

Enzymatic production of 1-butyl oleate ester using Rhizopus oryza cell system