title: Metal-Chelate Immobilization of Lipase onto Polyethylenimine Coated MCM-41 for Apple Flavor Synthesis.
abstract: An enzyme immobilized on a mesoporous silica nanoparticle can serve as a multiple catalyst for the synthesis of industrially useful chemicals. In this work, MCM-41 nanoparticles were coated with polyethylenimine (MCM-41@PEI) and further modified by chelation of divalent metal ions (M = Co2+, Cu2+, or Pd2+) to produce metal-chelated silica nanoparticles (MCM-41@PEI-M). Thermomyces lanuginosa lipase (TLL) was immobilized onto MCM-41, MCM-41@PEI, and MCM-41@PEI-M by physical adsorption. Maximum immobilization yield and efficiency of 75 ± 3.5 and 65 ± 2.7% were obtained for MCM@PEI-Co, respectively. The highest biocatalytic activity at extremely acidic and basic pH (pH = 3 and 10) values were achieved for MCM-PEI-Co and MCM-PEI-Cu, respectively. Optimum enzymatic activity was observed for MCM-41@PEI-Co at 75 °C, while immobilized lipase on the Co-chelated support retained 70% of its initial activity after 14 days of storage at room temperature. Due to its efficient catalytic performance, MCM-41@PEI-Co was selected for the synthesis of ethyl valerate in the presence of valeric acid and ethanol. The enzymatic esterification yield for immobilized lipase onto MCM-41@PEI-Co was 60 and 53%, respectively, after 24 h of incubation in n-hexane and dimethyl sulfoxide media. Graphical Abstract Divalent metal chelated polyethylenimine coated MCM-41 (MCM-41@PEI-M) was used for immobilization of Thermomyces lanuginosa lipase catalyzing green apple flavor preparation.
authors.affiliation: Department of Biomedical and Pharmaceutical Sciences, College of Pharmacy, University of Rhode Island, Kingston, RI, 02881, USA.
authors.forename: Armin
authors.initials: A
authors.lastname: Sadighi
authors.affiliation: Particulate Fluids Processing Centre, School of Chemistry, The University of Melbourne, Melbourne, VIC, 3010, Australia.
authors.forename: Seyed Farshad
authors.initials: SF
authors.lastname: Motevalizadeh
authors.affiliation: Department of Life Science Engineering, Faculty of New Sciences and Technologies, University of Tehran, Tehran, Iran.
authors.forename: Morteza
authors.initials: M
authors.lastname: Hosseini
authors.affiliation: Department of Chemistry, University of Zanjan, P.O. Box 45195-313, Zanjan, Iran.
authors.forename: Ali
authors.initials: A
authors.lastname: Ramazani
authors.affiliation: School of Natural Sciences, Griffith University, Nathan Campus, QLD, 4111, Australia.
authors.forename: Lena
authors.initials: L
authors.lastname: Gorgannezhad
authors.affiliation: Faculty of Pharmacy, Shahid Sadoughi University of Medical Sciences, Yazd, Iran.
authors.forename: Hamid
authors.initials: H
authors.lastname: Nadri
authors.affiliation: Division of Microbiology, Department of Pathobiology, School of Public Health, Tehran University of Medical Sciences sTUMS, Tehran, Iran.
authors.forename: Behnaz
authors.initials: B
authors.lastname: Deiham
authors.affiliation: Biosensor Research Center, Endocrinology and Metabolism Molecular-Cellular Sciences Institute, Tehran University of Medical Sciences, Tehran, Iran.
authors.forename: Mohammad Reza
authors.initials: MR
authors.lastname: Ganjali
authors.affiliation: Nanobiomaterials Group, Pharmaceutical Sciences Research Center, Tehran University of Medical Sciences, Tehran, 1417614411, Iran.
authors.forename: Abbas
authors.initials: A
authors.lastname: Shafiee
authors.affiliation: Department of Pharmaceutical Biotechnology, Faculty of Pharmacy and Biotechnology Research Center, Tehran University of Medical Sciences, P.O. Box 14155-6451, Tehran, 14176, Iran. faramarz@tums.ac.ir.
authors.forename: Mohammad Ali
authors.initials: MA
authors.lastname: Faramarzi
authors.affiliation: Nanobiomaterials Group, Pharmaceutical Sciences Research Center, Tehran University of Medical Sciences, Tehran, 1417614411, Iran. m-khoobi@tums.ac.ir.|Department of Pharmaceutical Biomaterials and Medical Biomaterials Research Center, Faculty of Pharmacy, Tehran University of Medical Sciences, Tehran, Iran. m-khoobi@tums.ac.ir.
authors.forename: Mehdi
authors.identifier: http://orcid.org/0000-0003-0962-7259
authors.initials: M
authors.lastname: Khoobi
mesh_terms: D000327:Adsorption; D002413:Cations, Divalent / Q000737:chemistry*; D060326:Chemistry Techniques, Synthetic; D004800:Enzymes, Immobilized / Q000737:chemistry* / Q000378:metabolism; D004951:Esterification; D032641:Eurotiales / Q000201:enzymology; D006863:Hydrogen-Ion Concentration; D008049:Lipase / Q000737:chemistry* / Q000378:metabolism; D008958:Models, Molecular; D053758:Nanoparticles / Q000737:chemistry*; D010421:Pentanoic Acids / Q000138:chemical synthesis*; D011094:Polyethyleneimine / Q000737:chemistry*; D011487:Protein Conformation; D012822:Silicon Dioxide / Q000737:chemistry*; D013499:Surface Properties; D013696:Temperature; D014631:Valerates
chemical_list: D002413:Cations, Divalent; D004800:Enzymes, Immobilized; C509968:MCM-41; D010421:Pentanoic Acids; D014631:Valerates; C000622367:ethyl valerate; D012822:Silicon Dioxide; D011094:Polyethyleneimine; D008049:Lipase; C038780:n-pentanoic acid
keywords: Esterification; Lipase immobilization; Mesoporous silica nanoparticles; Metal chelation; Polyethylenimine