Abstract

Inorganic biopolymer-based nanocomposites are useful for stabilizing lipases for enhanced catalytic performance and easy separation. Herein, we report the operational stability, regenerability, and thermodynamics studies of the ternary biogenic silica/magnetite/graphene oxide nanocomposite (SiO2/Fe3O4/GO) as a support for Candida rugosa lipase (CRL). The X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), field-electron scanning electron microscopy (FESEM), vibrating sample magnetometry (VSM), and nitrogen adsorption/desorption data on the support and biocatalyst corroborated their successful fabrication. XPS revealed the Fe3O4 adopted Fe2+ and Fe3+ oxidation states, while XRD data of GO yielded a peak at 2θ = 11.67°, with the SiO2/Fe3O4/GO revealing a high surface area (≈261 m2/g). The fourier transform infrared (FTIR) spectra affirmed the successful fabricated supports and catalyst. The half-life and thermodynamic parameters of the superparamagnetic immobilized CRL (CRL/SiO2/Fe3O4/GO) improved over the free CRL. The microwave-regenerated CRL/SiO2/Fe3O4/GO (≈82%) exhibited higher catalytic activity than ultrasonic-regenerated (≈71%) ones. Lower activation ( and higher deactivation energies ( were also noted for the CRL/SiO2/Fe3O4/GO (13.87 kJ/mol, 32.32 kJ/mol) than free CRL (15.26 kJ/mol, 27.60 kJ/mol). A peak at 4.28 min in the gas chromatograph-flame ionization detection (GC-FID) chromatogram of the purified ethyl valerate supported the unique six types of 14 hydrogen atoms of the ester (CAS: 539-82-2) in the proton nuclear magnetic resonance (1H-NMR) data. The results collectively demonstrated the suitability of SiO2/Fe3O4/GO in stabilizing CRL for improved operational stability and thermodynamics and permitted biocatalyst regenerability.

Highlights

  • This study examines the influence of biogenic SiO2 /Fe3 O4 /graphene oxide (GO) nanocomposites on the operational stability and thermodynamics of Candida rugosa lipase (CRL)/SiO2 /Fe3 O4 /GO compared to free CRL

  • The study demonstrates that the fabricated biogenic SiO2 /Fe3 O4 /GO support effecTheimproved study demonstrates the fabricated biogenic

  • The resultant biocatalyst successfully catalyzed higher yields of Ethyl valerate (EV) compared to free CRL

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Summary

Introduction

The graphene-based magnetic silica nanocomposite combination shows good prospects as a greener and sustainable biopolymer resource This is given the nanocomposite’s ability to stabilize lipases for higher catalytic activity and operational stability, as well as easier separation for recycling [1,2,3]. The ternary chitosan/chitin/Fe3 O4 covalently bound CRL produced 96% pentyl valerate and retained ≈90% initial activity after 40 days of storage [12] Another similar study using lipase conjugated to alginate/nanocellulose/montmorillonite composite produced 92.89% ethyl levulinate in just 6 h. CRL bound on the Fe3 O4 /SiO2 /PAMAM nanocomposite was reusable for seven successive reaction cycles, retaining 68% residual activity [14] Despite these advancements, the technology to fabricate novel ternary nanocomposites for lipase immobilization is still in its infancy. The obtained information could offer new insights into the SiO2 /Fe3 O4 /GO nanocomposite’s feasibility as support for other types of enzymes

Materials and Chemicals
Preparation of Support Systems
Characterization
Textural Properties and Pore Structure Analysis
Surface Morphological and Microstructural Analysis
Magnetic Behavior Analysis
Chemical Composition and Functional Group Analysis
Effect of Reaction Time on Esterification of Ethanol and Valeric Acid
Thermal Stability
Storage Stability
Regeneration Study
Characterization of Esterification Product
Statistical Analysis
Discussion
Odiffractogram
Textural Properties and
Effect of Reaction on EV
Thermal Stability and Half-Life
Short-Term Storage Stability
Short-Term
Kinetic Rate Constant and Activation Energy
Thermodynamics Parameters
Product Identification and Structural Elucidation of Ethyl Valerate
Findings
Conclusions
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