Historical perspective
Organic-inorganic hybrid nanoflowers: The known, the unknown, and the future

https://doi.org/10.1016/j.cis.2022.102780Get rights and content

Highlights

  • Synthesis and formation mechanisms of hybrid nanoflowers (HNFs) were reviewed.

  • The construction methods and uses of multi-component HNFs were outlined.

  • Applications of enzyme-free HNFs and their enzyme-like properties were described.

  • Biocatalytic, biosensing, and antimicrobial applications of HNFs were reviewed.

  • Effect of synthesis conditions on the specific properties of HNFs was described.

Abstract

Organic-inorganic hybrid nanoflowers (HNFs) are hierarchical flower-shaped microstructures that are assembled by nanoscale petal-like nanosheets composed of both organic and inorganic constituents. Generally, inorganic parts of HNFs are transition metal phosphates and organic components are mostly enzymes and proteins; however, non-protein molecules could be also used as organic phase in some types of newly described HNFs. Recent findings indicate that they are constructed through the coordination between organic and inorganic components. HNFs are mainly used for efficient biocatalysis and highly sensitive biosensing, while they have also some other noteworthy applications such as antimicrobial agents, antigen careers, and delivery platforms for anticancer drugs. It is believed that the high surface-to-volume ratio of HNFs could tackle mass transfer limitations leading to enhance the activity of their organic constituents. The environment-friendly route of synthesis and stabilization of biomolecules upon storage are the advantages of enzyme-based HNFs. In the present review, the focuses are on designs, preparations, formation mechanisms, and remarkable applications of the conventional forms and also magnetic, multi-component, and enzyme-free HNFs. Considering the fact that HNFs are in the early stages of development, the unknown aspects and future directions of research in this field are also discussed.

Section snippets

Definition, significance, and the history behind organic-inorganic hybrid nanoflowers (HNFs)

Organic-inorganic hybrid materials have drawn increasing attention in recent years as they simultaneously benefit from characteristics of both organic and inorganic constituents [1]. Flower-shaped organic-inorganic hybrid nanoflowers (HNFs) (Fig. 1) are one of the most popular hybrid materials that were accidentally discovered in 2012 by Zare’s group [2]. The inorganic component of HNFs is mainly composed of metal phosphates such as cobalt, copper, manganese, zinc, ferrous, and calcium salts.

One-pot conventional biomineralization method

As mentioned, HNFs were firstly discovered by Zare’s group after an accidental addition of copper sulfate to phosphate-buffered saline (PBS) (pH 7.4) containing bovine serum albumin (BSA) followed by an incubation of 3 days at room temperature [2]. The most commonly used method for preparing HNFs is nearly identical to the research of Zare's group. For instance, phosphotriesterase (PTE)@Cu3(PO4)2•HNFs were synthesized by the incubation of a mixture containing phosphate buffer, PTE, and CuSO4 at

Mechanism of HNFs formation

As discussed, HNFs have been synthesized by a number of methods; however, all of the methods are based on the coordination between organic and inorganic components. It is believed that the formation mechanism of HNFs involves nucleation, coordination, precipitation, and self-assembly [2]. At first, the spontaneous interfacial reaction between metal ions and negatively-charged phosphate groups results in the formation of metal phosphate nanocrystals. The primary crystals participate in

Innovations in designing HNFs

Incorporating a wide range of organic substances in the structure of HNFs to achieve novel or desired specific properties is a developing concern. Most reported HNFs are fabricated by incorporating enzymes as the organic and copper phosphate as the inorganic building blocks, as previously mentioned. Designing distinct and innovative HNFs is favorable for enhancing their biocatalytic functions such as enzyme stability, activity, and reusability. Therefore, enzyme-free, magnetic, and

HNFs-mediated biocatalysis

Both enzyme-loaded and enzyme-free HNFs can be applied as biocatalysts in many biochemical reactions, and the incorporation of enzymes inside HNFs increases their catalytic activity, reusability, and stability. Magnetic laccase-loaded HNFs with Cu3(PO4)2 were designed to degrade bisphenol A [98]. Laccase activity inside MHNFs was 3.3 times higher than that of the free enzyme, and the immobilized laccase retained 70% of its initial activity after 8 reuse cycles. The stability of the enzyme

Concluding remarks and future perspectives

HNFs have received remarkable attention during the past decade regarding their facile synthesis, flower-shaped structures, high surface property, and potential applications. Wide ranges of organic molecules and metal phosphates have been incorporated into the structures of HNFs. Based on recent evidences, it is proposed that the coordination of oxygen atoms from an organic constituent as well as nitrogen atoms with metal ions of an inorganic part is another possible type of mechanism involved

CRediT authorship contribution statement

Hossein Jafari-Nodoushan: Conceptualization, Methodology, Investigation, Writing – original draft, Visualization, Writing – review & editing. Somayeh Mojtabavi: Formal analysis, Data curation, Writing – original draft. Mohammad Ali Faramarzi: Supervision, Conceptualization, Methodology, Resources, Data curation, Writing – review & editing, Project administration, Funding acquisition. Nasrin Samadi: Supervision, Formal analysis, Writing – review & editing, Conceptualization, Software,

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

This work was financially supported by the grant No. 1400-2-104-53421 from Faculty of Pharmacy, Tehran University of Medical Sciences, Tehran, Iran. The study is a part of the Ph.D. thesis of Dr. H. Jafari-Nodoushan.

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