Epoxidation of (<i>R</i>)-(+)-Limonene to 1,2-Limonene Oxide Mediated by Low-Cost Immobilized <i>Candida antarctica</i> Lipase Fraction B

Melchiors, Marina de Souza; Vieira, Thayne Y.; Pereira, Luiz P. S.; Carciofi, Bruno Augusto Mattar; Araújo, Pedro Henrique Hermes de; Oliveira, Débora de; Sayer, Cláudia

doi:10.1021/acs.iecr.9b02168

Cited by 18 publications

(10 citation statements)

References 45 publications

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“…While the use of epoxide reagents and resins is commonplace in both academic and industrial laboratories, the structure–reactivity relationships we discovered over the years easily translate to a larger set of (co)polymerization reactions. To make the synthesis of polymers derived from biobased epoxides more sustainable, environmentally more benign conditions for the epoxidation of alkene-derived feedstocks are warranted, such as in enzymatic oxidations where H 2 O 2 is used as the reagent …”

Section: Outlook and Opportunitiesmentioning

confidence: 99%

Catalyst Engineering Empowers the Creation of Biomass-Derived Polyesters and Polycarbonates

Brandolese

Kleij

2022

Acc. Chem. Res.

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Conspectus The introduction of circular principles in chemical manufacturing will drastically change the way everyday plastics are produced, thereby affecting several aspects of the respective value chains in terms of raw feedstock, recyclability, and cost. The ultimate aim is to ensure a paradigm shift toward plastic-based (consumer) materials that overall can offer a more attractive and sustainable carbon footprint, which is an important requisite from a societal, political, and eventually economical point of view. To realize this important milestone, it is vitally important to control the polymerization processes associated with the creation of novel sustainable materials. In this respect, we realized that expanding the portfolio of biomass-derived monomers may indeed create an impetus for atom circularity; however, the often sterically congested nature of biomass-derived monomers minimizes the ability of previously developed catalysts to activate and transform these precursors. Our motivation was thus spurred by an apparent lack of catalysts suitable for addressing the conversion of such biomonomers, as we realized the potential that new catalytic processes could have to advance and contribute to the development of sustainable materials produced from polycarbonates and polyesters. These two classes of polymers represent crucial ingredients of important and large-scale consumer products and are therefore ideal fits for implementing new catalytic protocols that enable a gradual transition to plastic materials with an improved carbon footprint. When we started our research expedition, the field was dominated by metal catalysts that incorporated preferred, and in some cases even privileged, ligand backbones (such as salens) able to mediate both ring-opening and ring-opening copolymerization manifolds. One major drawback of these aforementioned catalysts is their rather rigid nature, a feature that reduces their ability to act as adaptive systems, especially in cases where bulky monomers are involved. While our initial focus was on the utilization of sustainable metal salen complexes (M = Zn, Fe) for the activation of small cyclic ethers, which are privileged monomers for polyester and polycarbonate production, we were rapidly confronted with severe limitations related to their inability to activate a wider range of complex epoxides and oxetanes, which was imparted by the planar coordination geometry of the salen ligand in most of its applied metal complexes. In our quest to find a catalytically more effective metal complex with the ability to electronically and sterically tune its substrate-binding and substrate-activation potential, we identified aminotriphenolates as structurally versatile, easily accessible, and scalable ligands for various earth-abundant metal cations. Moreover, the ligand backbone allows for switchable coordination environments around the metal centers, thus offering the necessary adaptation in substrate activation events. This Account describes how Al(III)- and Fe(III)-centered aminotriph...

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Section: Outlook and Opportunitiesmentioning

confidence: 99%

Catalyst Engineering Empowers the Creation of Biomass-Derived Polyesters and Polycarbonates

Brandolese

Kleij

2022

Acc. Chem. Res.

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“…Lipases can catalyze a very wide range of reactions, covering not only the formation and hydrolysis of an ester bond, such as esterification or transesterification between an ester and an alcohol or an acid, as well as between two esters, but also amidation, aminolysis, aldol concentration, Michael addition, opening of lactone rings, epoxidation, etc. [ 45 , 145 , 146 , 147 , 148 , 149 , 150 ]. Lipases can exhibit enzymatic activity in various media, including acidic, neutral and alkaline aqueous; aqueous–organic solutions; organic solvents; or ionic liquids, and in the presence of detergents [ 151 ].…”

Section: Enzymes and Polymers Produced With Themmentioning

confidence: 99%

Prospects of Using Biocatalysis for the Synthesis and Modification of Polymers

Nikulin

Švedas

2021

Molecules

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Trends in the dynamically developing application of biocatalysis for the synthesis and modification of polymers over the past 5 years are considered, with an emphasis on the production of biodegradable, biocompatible and functional polymeric materials oriented to medical applications. The possibilities of using enzymes not only as catalysts for polymerization but also for the preparation of monomers for polymerization or oligomers for block copolymerization are considered. Special attention is paid to the prospects and existing limitations of biocatalytic production of new synthetic biopolymers based on natural compounds and monomers from biomass, which can lead to a huge variety of functional biomaterials. The existing experience and perspectives for the integration of bio- and chemocatalysis in this area are discussed.

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“…The other advantage of using octanoic acid is that it does not affect the stability of the enzyme, which has been previously discussed by many researchers. 50 , 51 As the concentration of octanoic acid increases from 10 to 50 mM, the conversion of limonene oxide increased. However, as the concentration was further increased to 75 mM, conversion decreased.…”

Section: Optimization Studiesmentioning

confidence: 99%

“…The selectivity of limonene monoxide was ∼85%. The literature states the possible formation of other byproducts such as 1,2 -8,9-limonene diepoxide. , The activation energy was calculated from the Arrhenius plot as 3.264 kcal/mole (Supporting Information Figure S1), which falls in the range of enzymatic reactions.…”

Section: Optimization Studiesmentioning

confidence: 99%

Chemoenzymatic Epoxidation of Limonene Using a Novel Surface-Functionalized Silica Catalyst Derived from Agricultural Waste

Salvi

Yadav

2020

ACS Omega

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Limonene is one of the most important terpenes having wide applications in food and fragrance industries. The epoxide of limonene, limonene oxide, finds important applications as a versatile synthetic intermediate in the chemical industry. Therefore, attempts have been made to synthesize limonene oxide using eco-friendly processes because of stringent regulations on its production. In this regard, we have attempted to synthesize it using a cost-effective and eco-friendly process. Chemoenzymatic epoxidation of limonene to limonene oxide was carried out using in situ generation of peroxy octanoic acid from octanoic acid and H 2 O 2 . In this study, agricultural-waste rice husk ash (RHA)-derived silica was surface-functionalized using (3-aminopropyl) triethoxysilane (APTS), which was cross-linked using glutaraldehyde for immobilization of Candida antarctica lipase B. Furthermore, the immobilized enzyme was entrapped in calcium alginate beads to avoid enzyme leaching. Thus, limonene oxide was prepared using this catalyst under conventional and microwave heating. The microwave irradiation intensifies the process, reducing the reaction time under the same conditions. Maximum conversion of limonene to limonene oxide of 75.35 ± 0.98% was obtained in 2 h at 50 °C using a microwave power of 50 W. In the absence of microwave irradiation, the conventional heating gave 44.6 ± 1.14% conversion in 12 h. The reaction mechanism was studied using the Lineweaver–Burk plot, which follows a ternary complex mechanism with inhibition due to peroxyoctanoic acid (in other words H 2 O 2 ). The prepared catalyst shows high reusability and operational stability up to four cycles.

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Epoxidation of (R)-(+)-Limonene to 1,2-Limonene Oxide Mediated by Low-Cost Immobilized Candida antarctica Lipase Fraction B

Cited by 18 publications

References 45 publications

Catalyst Engineering Empowers the Creation of Biomass-Derived Polyesters and Polycarbonates

Catalyst Engineering Empowers the Creation of Biomass-Derived Polyesters and Polycarbonates

Prospects of Using Biocatalysis for the Synthesis and Modification of Polymers

Chemoenzymatic Epoxidation of Limonene Using a Novel Surface-Functionalized Silica Catalyst Derived from Agricultural Waste

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