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固定在功能化超顺磁性少层氧化石墨烯上的脂肪酶作为从生物油生产生物柴油的高效纳米生物催化剂。

Lipase immobilized on functionalized superparamagnetic few-layer graphene oxide as an efficient nanobiocatalyst for biodiesel production from bio-oil.

作者信息

Nematian Tahereh, Shakeri Alireza, Salehi Zeinab, Saboury Ali Akbar

机构信息

1Department of Applied Chemistry, School of Chemistry, College of Science, University of Tehran, Tehran, Iran.

2Department of Biotechnology Engineering, School of Chemical Engineering, College of Engineering, University of Tehran, Tehran, Iran.

出版信息

Biotechnol Biofuels. 2020 Mar 20;13:57. doi: 10.1186/s13068-020-01688-x. eCollection 2020.

Abstract

BACKGROUND

Microalgae, due to its well-recognized advantages have gained renewed interest as potentially good feedstock for biodiesel. Production of fatty acid methyl esters (FAMEs) as a type of biodiesel was carried out from bio-oil. Biodiesel was produced in the presence of nano-biocatalysts composed of immobilized lipase on functionalized superparamagnetic few-layer graphene oxide via a transesterification reaction. A hybrid of few-layer graphene oxide and FeO (MGO) was prepared and characterized. The MGO was functionalized with 3-aminopropyl triethoxysilane (MGO-AP) as well as with a couple of AP and glutaraldehyde (MGO-AP-GA). The lipase (ROL) was immobilized on MGO and MGO-AP using electrostatic interactions as well as on MGO-AP-GA using covalent bonding. The supports, MGO, MGO-AP, and MGO-AP-GA, as well as nano-biocatalyst, ROL/MGO, ROL/MGO-AP, and ROL/MGO-AP-GA, were characterized using FESEM, VSM, FTIR, and XRD. The few-layer graphene oxide was characterized using AFM and the surface charge of supports was evaluated with the zeta potential technique. The nano-biocatalysts assay was performed with an evaluation of kinetic parameters, loading capacity, relative activity, time-course thermal stability, and storage stability. Biodiesel production was carried out in the presence of nano-biocatalysts and their reusability was evaluated in 5 cycles of transesterification reaction.

RESULTS

The AFM analysis confirmed the few-layer structure of graphene oxide and VSM also confirmed that all supports were superparamagnetic. The maximum loading of ROL (70.2%) was related to MGO-AP-GA. The highest biodiesel conversion of 71.19% achieved in the presence of ROL/MGO-AP-GA. Furthermore, this nano-biocatalyst could maintain 58.77% of its catalytic performance after 5 cycles of the transesterification reaction and was the best catalyst in the case of reusability.

CONCLUSIONS

In this study, the synthesized nano-biocatalyst based on bare and functionalized magnetic graphene oxide was applied and optimized in the process of converting microalgae bio-oil to biodiesel for the first time and compared with bare lipase immobilized on magnetic nanoparticles. Results showed that the loading capacity, kinetic parameters, thermal stability, and storage stability improved by the functionalization of MGO. The biocatalysts, which were prepared via covalent bonding immobilization of enzyme generally, showed better characteristics.

摘要

背景

微藻因其公认的优势,作为生物柴油潜在的优质原料重新引起了人们的关注。脂肪酸甲酯(FAMEs)作为一种生物柴油,是由生物油生产的。在由固定在功能化超顺磁性少层氧化石墨烯上的脂肪酶组成的纳米生物催化剂存在下,通过酯交换反应生产生物柴油。制备并表征了少层氧化石墨烯与FeO的混合物(MGO)。MGO用3-氨丙基三乙氧基硅烷(MGO-AP)以及AP和戊二醛的组合(MGO-AP-GA)进行功能化。脂肪酶(ROL)通过静电相互作用固定在MGO和MGO-AP上,并通过共价键固定在MGO-AP-GA上。使用场发射扫描电子显微镜(FESEM)、振动样品磁强计(VSM)、傅里叶变换红外光谱仪(FTIR)和X射线衍射仪(XRD)对载体MGO、MGO-AP和MGO-AP-GA以及纳米生物催化剂ROL/MGO、ROL/MGO-AP和ROL/MGO-AP-GA进行了表征。使用原子力显微镜(AFM)对少层氧化石墨烯进行了表征,并使用zeta电位技术评估了载体的表面电荷。通过评估动力学参数、负载能力、相对活性、时间进程热稳定性和储存稳定性对纳米生物催化剂进行了测定。在纳米生物催化剂存在下进行生物柴油生产,并在5个酯交换反应循环中评估了它们的可重复使用性。

结果

AFM分析证实了氧化石墨烯的少层结构,VSM也证实了所有载体都是超顺磁性的。ROL的最大负载量(70.2%)与MGO-AP-GA相关。在ROL/MGO-AP-GA存在下,生物柴油的最高转化率达到71.19%。此外,这种纳米生物催化剂在5个酯交换反应循环后仍能保持其催化性能的58.77%,是可重复使用性方面最好的催化剂。

结论

在本研究中,首次将基于裸露和功能化磁性氧化石墨烯合成的纳米生物催化剂应用于微藻生物油转化为生物柴油的过程并进行优化,并与固定在磁性纳米颗粒上的裸露脂肪酶进行了比较。结果表明,MGO的功能化提高了负载能力、动力学参数、热稳定性和储存稳定性。一般通过酶的共价键固定制备的生物催化剂表现出更好的特性。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4bc3/7082915/8fe3e72e6127/13068_2020_1688_Fig1_HTML.jpg

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